Imaging element, stacked-type imaging element, solid-state imaging device, and driving method for solid-state imaging device

ABSTRACT

An imaging device is provided. The imaging device may include a substrate having a first photoelectric conversion unit and a second photoelectric conversion unit at a light-incident side of the substrate. The second photoelectric conversion unit may include a photoelectric conversion layer, a first electrode, a second electrode above the photoelectric conversion layer, a third electrode, and an insulating material between the third electrode and the photoelectric conversion layer, wherein a portion of the insulating material is between the first electrode and the third electrode.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation of U.S. patent application Ser. No.15/553,653 filed Aug. 25, 2017, which is a national stage applicationunder 35 U.S.C. 371 and claims the benefit of PCT Application No.PCT/JP2017/007819 having an international filing date of Feb. 28, 2017,which designated the United States, which PCT application claimed thebenefit of Japanese Patent Application No. 2016-038777 filed Mar. 1,2016, and Japanese Patent Application No. 2016-193919 filed Sep. 30,2016, the disclosures of which are incorporated herein by reference intheir entirety. This application is also related to U.S. patentapplication Ser. No. 15/796,545 filed Oct. 27, 2017, now U.S. Pat. No.10,468,451.

TECHNICAL FIELD

The present disclosure relates to an imaging element, a stacked-typeimaging element, a solid-state imaging device, and a driving method fora solid-state imaging device.

BACKGROUND ART

Imaging elements using organic semiconductor materials for photoelectricconversion layers can photoelectrically convert specific colors(wavelength bands). Furthermore, due to the characteristic, in the caseof using the imaging elements as imaging elements in solid-state imagingdevices, it is possible to achieve a structure (stacked-type imagingelement) of sub pixels where each subpixel is configured as acombination of an on-chip color filter (OCCF) and an imaging element,and the subpixels are arranged two-dimensionally (for example, refer toJP 2011-138927 A). In addition, since a demosaic process is notnecessary, there is an advantage in that false color does not occur.Note that, in the description hereinafter, in some cases, an imagingelement which is provided on or above a semiconductor substrate andincludes a photoelectric conversion unit is, for the convenience ofdescription, referred to as a “first-type imaging element;” aphotoelectric conversion unit constituting the first-type imagingelement is, for the convenience of description, referred to as a“first-type photoelectric conversion unit;” an imaging element providedin a semiconductor substrate is, for the convenience of description,referred to as a “second-type imaging element;” and a photoelectricconversion unit constituting the second-type imaging element is, for theconvenience of description, referred to as a “second-type photoelectricconversion unit.”

A structure example of a stacked-type imaging element (stacked-typesolid-state imaging device) in the related art is illustrated in FIG.49. In the example illustrated in FIG. 49, a third photoelectricconversion unit 331 and a second photoelectric conversion unit 321 aresecond-type photoelectric conversion units constituting a third imagingelement 330 and a second imaging element 320, respectively, assecond-type imaging elements that are formed in a semiconductorsubstrate 370 to be stacked. In addition, a first photoelectricconversion unit 311 is a first-type photoelectric conversion unitarranged above the semiconductor substrate 370 (specifically, above thesecond imaging element 320). The first photoelectric conversion unit 311is configured to include a first electrode 311, a photoelectricconversion layer 315 made of an organic material, and a second electrode316 and constitutes a first imaging element 310 as a first-type imagingelement. Due to a difference in the absorption coefficient, the secondphotoelectric conversion unit 321 and the third photoelectric conversionunit 331 photoelectrically convert, for example, blue light and redlight, respectively. In addition, the first photoelectric conversionunit 311 photoelectrically converts, for example, green light.

Charges generated through photoelectric conversion in the secondphotoelectric conversion unit 321 and the third photoelectric conversionunit 331 are temporarily stored in the second photoelectric conversionunit 321 and the third photoelectric conversion unit 331 and, afterthat, are transferred to the second floating diffusion layer (FloatingDiffusion) FD₂ and the third floating diffusion layer FD₃ by avertical-type transistor (gate portion 322 is illustrated) and atransfer transistor (gate portion 332 is illustrated), respectively. Thecharges are further output to an external reading circuit (not shown).The transistors and the floating diffusion layers FD₂ and FD₃ are alsoformed in the semiconductor substrate 370.

Charges generated through photoelectric conversion in the firstphotoelectric conversion unit 311 are stored through a contact holeportion 361 and a wire line layer 362 to a first floating diffusionlayer FD₁ formed in the semiconductor substrate 370. The firstphotoelectric conversion unit 311 is also connected through the contacthole portion 361 and the wire line layer 362 to a gate portion 318 of anamplification transistor which converts a charge amount to a voltage.Furthermore, the first floating diffusion layer FD₁ constitutes aportion of a reset transistor (gate portion 317 is illustrated). Notethat reference numeral 371 denotes an element isolation region;reference numeral 372 denotes an oxide film formed on a surface of thesemiconductor substrate 370; reference numerals 376 and 381 denoteinterlayer insulating layers; reference numeral 383 denotes a protectivelayer; and reference numeral 390 denotes an on-chip microlens.

CITATION LIST Patent Literature [PTL 1]

-   JP 2011-138927 A

SUMMARY OF INVENTION Technical Problem

However, the charges generated through photoelectric conversion in thesecond photoelectric conversion unit 321 and the third photoelectricconversion unit 331 are temporarily stored in the second photoelectricconversion unit 321 and the third photoelectric conversion unit 331 and,after that, are transferred to the second floating diffusion layer FD₂and the third floating diffusion layer FD₃, respectively. Therefore, itis possible to completely deplete the second photoelectric conversionunit 321 and the third photoelectric conversion unit 331. However, thecharges generated through photoelectric conversion in the firstphotoelectric conversion unit 311 are directly stored in the firstfloating diffusion layer FD₁. Therefore, it is difficult to completelydeplete the first photoelectric conversion unit 311. As a result, kTCnoise is increased, random noise is deteriorated, and thus, imagequality in the imaging is deteriorated.

The present disclosure provides an imaging element where a photoelectricconversion unit is arranged on or above a semiconductor substrate andwhich has a configuration and a structure capable of suppressingdeterioration in imaging quality, a stacked-type imaging elementconfigured with the imaging element, a solid-state imaging deviceincluding the imaging element or the stacked-type imaging element, and adriving method for a solid-state imaging device.

Solution of Invention

According to a first embodiment of the present disclosure, an imagingdevice is provided. The imaging device may include a substrate includinga first photoelectric conversion unit, and a second photoelectricconversion unit at a light-incident side of the substrate. The secondphotoelectric conversion unit may include a photoelectric conversionlayer, a first electrode, a second electrode above the photoelectricconversion layer, a third electrode, and an insulating material betweenthe third electrode and the photoelectric conversion layer, wherein aportion of the insulating material is between the first electrode andthe third electrode.

According to a second embodiment of the present disclosure, anelectronic apparatus is provided, the electronic apparatus including animaging device which includes a substrate including a firstphotoelectric conversion unit, and a second photoelectric conversionunit at a light-incident side of the substrate. The second photoelectricconversion unit may include a photoelectric conversion layer, a firstelectrode, a second electrode above the photoelectric conversion layer,a third electrode, and an insulating material between the thirdelectrode and the photoelectric conversion layer, wherein a portion ofthe insulating material is between the first electrode and the thirdelectrode, and a lens configured to direct light onto a surface of theimaging device.

According to a third embodiment of the present disclosure, a method ofdriving an imaging device is provided. The method may include applying afirst potential to a charge storage electrode during a charging period,applying a second potential to a first electrode during a chargingperiod, wherein the first potential is greater than the secondpotential, applying a third potential to the charge storage electrodeduring a charge transfer period; and

applying a fourth potential to the first electrode during the chargetransfer period, wherein the fourth potential is greater than the thirdpotential. In some embodiments,

the imaging device includes a substrate including a first photoelectricconversion unit, and a second photoelectric conversion unit at alight-incident side of the substrate. The second photoelectricconversion unit may include a photoelectric conversion layer, the firstelectrode, a second electrode above the photoelectric conversion layer,

the charge storage electrode, and an insulating material between thecharge storage electrode and the photoelectric conversion layer, whereina portion of the insulating material is between the first electrode andthe charge storage electrode.

Advantage Effects of Invention

In an imaging element according to an embodiment of the presentdisclosure, an imaging element according to an embodiment of the presentdisclosure constituting a stacked-type imaging element according to anembodiment of the present disclosure, or an imaging element according toan embodiment of the present disclosure constituting a solid-stateimaging device according to a first or second embodiment of the presentdisclosure (in some cases, hereinafter, these imaging elements arecollectively referred to as an “imaging element or the like according toan embodiment of the present disclosure”), since a charge storageelectrode, which is arranged to be separated from a first electrode andis arranged to face a photoelectric conversion layer with an insulatinglayer interposed therebetween, is included, charges can be stored in thephotoelectric conversion layer when the photoelectric conversion unit isilluminated with light and the light is photoelectrically converted inthe photoelectric conversion unit. Therefore, at the time of a startingexposure, by completely depleting a charge storage unit, it is possibleto erase the charges. As a result, it is possible to suppress theoccurrence of the phenomenon of an increase in kTC noise, deteriorationin random noise, and deterioration in image quality in the imaging. In adriving method for a solid-state imaging device according to anembodiment of the present disclosure, each imaging element has astructure where light incident from a second electrode side is notincident on the first electrode, and thus, in all the imaging elements,at one time, charges are stored in the photoelectric conversion layer,and the charges of the first electrode are ejected to the outside sothat it is possible to reliably perform resetting the first electrodesin all the imaging elements simultaneously. Subsequently, in all theimaging elements, at one time, the charges stored in the photoelectricconversion layer are transferred to the first electrode, and after thecompletion of transfer, the charges transferred to the first electrodesin the respective imaging elements are sequentially read out. Therefore,a so-called global shutter function can be easily implemented. Note thatthe effects disclosed in the specification are exemplary ones but notlimitative ones, and there may also be additional effects.

BRIEF DESCRIPTION OF DRAWINGS

FIG. 1A is a schematic partial cross-sectional view of an imagingelement and a stacked-type imaging element of Example 1.

FIG. 1B is a schematic partial cross-sectional view of an imagingelement and a stacked-type imaging element of Example 1.

FIG. 1C is a schematic partial cross-sectional view of an imagingelement and a stacked-type imaging element of Example 1.

FIG. 1D is a schematic partial cross-sectional view of an imagingelement and a stacked-type imaging element of Example 1.

FIG. 2 is an equivalent circuit diagram of the imaging element and thestacked-type imaging element of Example 1.

FIG. 3 is an equivalent circuit diagram of the imaging element and thestacked-type imaging element of Example 1.

FIG. 4 is a schematic layout view of a first electrode and a chargestorage electrode constituting the imaging element of Example 1 andtransistors constituting a control unit.

FIG. 5 is a diagram illustrating potential states of components in anoperation period of the imaging element of Example 1.

FIG. 6 is a schematic layout view of the first electrode and the chargestorage electrode constituting the imaging element of Example 1.

FIG. 7 is a schematic perspective view of the first electrode, thecharge storage electrode, a second electrode, and a contact hole portionconstituting the imaging element of Example 1.

FIG. 8 is a conceptual diagram of a solid-state imaging device ofExample 1.

FIG. 9 is an equivalent circuit diagram of a modified example of theimaging element and the stacked-type imaging element of Example 1.

FIG. 10 is a schematic layout view of a first electrode and a chargestorage electrode constituting the modified example of the imagingelement of Example 1 illustrated in FIG. 9 and transistors constitutinga control unit.

FIG. 11 is a schematic partial cross-sectional view of an imagingelement and a stacked-type imaging element of Example 2.

FIG. 12 is a schematic partial cross-sectional view of an imagingelement and a stacked-type imaging element of Example 3.

FIG. 13 is a schematic partial cross-sectional view of a modifiedexample of the imaging element and the stacked-type imaging element ofExample 3.

FIG. 14 is a schematic partial cross-sectional view of another modifiedexample of the imaging element of Example 3.

FIG. 15A is a schematic partial cross-sectional view of another modifiedexample of the imaging element of Example 3.

FIG. 15B is a schematic partial cross-sectional view of another modifiedexample of the imaging element of Example 3.

FIG. 15C is a schematic partial cross-sectional view of another modifiedexample of the imaging element of Example 3.

FIG. 15D is a schematic partial cross-sectional view of another modifiedexample of the imaging element of Example 3.

FIG. 16 is a schematic partial cross-sectional view of a portion of animaging element and a stacked-type imaging element of Example 4,

FIG. 17 is an equivalent circuit diagram of the imaging element and thestacked-type imaging element of Example 4.

FIG. 18 is an equivalent circuit diagram of the imaging element and thestacked-type imaging element of Example 4.

FIG. 19 is a schematic layout view of a first electrode, a transfercontrol electrode, and a charge storage electrode constituting theimaging element of Example 4 and transistors constituting a controlunit.

FIG. 20 is a diagram illustrating potential states of components in anoperation period of the imaging element of Example 4.

FIG. 21 is a diagram illustrating potential states of components inanother operation period of the imaging element of Example 4.

FIG. 22 is a schematic layout view of the first electrode, the transfercontrol electrode, and the charge storage electrode constituting theimaging element of Example 4.

FIG. 23 is a schematic perspective view of the first electrode, thetransfer control electrode, the charge storage electrode, and a secondelectrode, and a contact hole portion constituting the imaging elementof Example 4.

FIG. 24 is a schematic layout view of a first electrode, a transfercontrol electrode, and a charge storage electrode constituting amodified example of the imaging element of Example 4 and transistorsconstituting a control unit.

FIG. 25 is a schematic partial cross-sectional view of a portion of animaging element and a stacked-type imaging element of Example 5.

FIG. 26 is a schematic layout view of a first electrode, a chargestorage electrode, and a charge ejection electrode constituting theimaging element of Example 5.

FIG. 27 is a schematic perspective view of the first electrode, thecharge storage electrode, the charge ejection electrode, a secondelectrode, and a contact hole portion constituting the imaging elementof Example 5.

FIG. 28 is a schematic partial cross-sectional view of a portion of animaging element and a stacked-type imaging element of Example 6.

FIG. 29 is an equivalent circuit diagram of the imaging element and thestacked-type imaging element of Example 6.

FIG. 30 is an equivalent circuit diagram of the imaging element and thestacked-type imaging element of Example 6.

FIG. 31 is a schematic layout view of a first electrode and a chargestorage electrode constituting the imaging element of Example 6 andtransistors constituting a control unit.

FIG. 32 is a diagram illustrating potential states of components in anoperation period of the imaging element of Example 6.

FIG. 33 is a diagram illustrating potential states of components inanother operation period (transfer period) of the imaging element ofExample 6.

FIG. 34 is a schematic layout view of the first electrode and the chargestorage electrode constituting the imaging element of Example 6.

FIG. 35 is a schematic perspective view of the first electrode, thecharge storage electrode, a second electrode, and a contact hole portionconstituting the imaging element of Example 6.

FIG. 36 is a schematic layout view of a first electrode and a chargestorage electrode constituting a modified example of the imaging elementof Example 6.

FIG. 37 is a schematic partial cross-sectional view of another modifiedexample of the imaging element and the stacked-type imaging element ofExample 1.

FIG. 38 is a schematic partial cross-sectional view of another modifiedexample of the imaging element and the stacked-type imaging element ofExample 1.

FIG. 39A is a schematic enlarged partial cross-sectional view of aportion of a first electrode and the like of another modified example ofthe imaging element and the stacked-type imaging element of Example 1.

FIG. 39B is a schematic enlarged partial cross-sectional view of aportion of a first electrode and the like of another modified example ofthe imaging element and the stacked-type imaging element of Example 1.

FIG. 39C is a schematic enlarged partial cross-sectional view of aportion of a first electrode and the like of another modified example ofthe imaging element and the stacked-type imaging element of Example 1.

FIG. 40 is a schematic enlarged partial cross-sectional view of aportion of a charge ejection electrode and the like of another modifiedexample of the imaging element and the stacked-type imaging element ofExample 5.

FIG. 41 is a schematic partial cross-sectional view of another modifiedexample of the imaging element and the stacked-type imaging element ofExample 1.

FIG. 42 is a schematic partial cross-sectional view of another modifiedexample of the imaging element and the stacked-type imaging element ofExample 1.

FIG. 43 is a schematic partial cross-sectional view of another modifiedexample of the imaging element and the stacked-type imaging element ofExample 1.

FIG. 44 is a schematic partial cross-sectional view of another modifiedexample of the imaging element and the stacked-type imaging element ofExample 4.

FIG. 45 is a schematic partial cross-sectional view of another modifiedexample of the imaging element and the stacked-type imaging element ofExample 1.

FIG. 46A is a schematic partial cross-sectional view of another modifiedexample of the imaging element and the stacked-type imaging element ofExample 1.

FIG. 46B is a schematic partial cross-sectional view of another modifiedexample of the imaging element and the stacked-type imaging element ofExample 1.

FIG. 46C is a schematic partial cross-sectional view of another modifiedexample of the imaging element and the stacked-type imaging element ofExample 1.

FIG. 46D is a schematic partial cross-sectional view of another modifiedexample of the imaging element and the stacked-type imaging element ofExample 1.

FIG. 47 is a schematic partial cross-sectional view of another modifiedexample of the imaging element and the stacked-type imaging element ofExample 4.

FIG. 48 is a conceptual diagram of an example of an electronic apparatus(camera) using a solid-state imaging device configured with the imagingelement and the stacked-type imaging element according to an embodimentof the present disclosure.

FIG. 49 is a conceptual diagram of a stacked-type imaging element(stacked-type solid-state imaging device) in the related art.

DESCRIPTION OF EMBODIMENTS

Hereinafter, the present disclosure will be described on the basis ofExamples with reference to the drawings. However, the present disclosureis not limited to the Examples, and various numeric values and materialsin the Examples are exemplary ones. Note that the description is made inthe order as follows.

1. Overall Description of Imaging Element according to an Embodiment ofthe Present Disclosure, Stacked-Type Imaging Element according to anEmbodiment of the Present Disclosure, Solid-State Imaging Deviceaccording to First or Second Embodiment of the Present Disclosure, andDriving Method for Solid-State Imaging Device according to an Embodimentof the Present Disclosure

2. Example 1 (Imaging Element according to an Embodiment of the PresentDisclosure, Stacked-Type Imaging Element according to an Embodiment ofthe Present Disclosure, and Solid-State Imaging Device according toSecond Embodiment of the Present Disclosure)

3. Example 2 (Modification of Example 1)

4. Example 3 (Modification of Examples 1 and 2)

5. Example 4 (Modification of Examples 1 to 3, Imaging Element HavingTransfer Control Electrode)

6. Example 5 (Modification of Examples 1 to 4, Imaging Element HavingCharge Ejection Electrode)

7. Example 6 (Modification of Examples 1 to 5, Imaging Element HavingCharge Storage Electrode Segments)

8. Others

<Overall Description of Imaging Element according to an Embodiment ofthe Present Disclosure, Stacked-Type Imaging Element according to anEmbodiment of the Present Disclosure, Solid-State Imaging Deviceaccording to First or Second Embodiment of the Present Disclosure, andDriving Method for Solid-State Imaging Device according to an Embodimentof the Present Disclosure >

In an imaging element or the like according to an embodiment of thepresent disclosure, the imaging element may further include asemiconductor substrate, and a photoelectric conversion unit may bearranged above the semiconductor substrate. Note that a first electrode,a charge storage electrode, and a second electrode are connected to adriving circuit described later.

The second electrode located in a light incidence side may be commonlyprovided to a plurality of imaging elements. Namely, the secondelectrode may be configured as a so-called solid electrode. Thephotoelectric conversion layer may be commonly provided to a pluralityof the imaging elements. Namely, one layer of the photoelectricconversion layer may be formed for a plurality of the imaging elementsor may be formed for every imaging element.

Furthermore, in the imaging element or the like according to anembodiment of the present disclosure including various exemplary formsand configurations described above, the first electrode may be formed toextend in an opening portion provided to the insulating layer to beconnected to the photoelectric conversion layer. Alternatively, thephotoelectric conversion layer may be formed to extend in the openingportion provided to the insulating layer to be connected to the firstelectrode. In this case, the imaging element or the like may beconfigured to have a form where an edge of a top surface of the firstelectrode is covered with the insulating layer, the first electrode isexposed to a bottom surface of the opening portion, and when a surfaceof the insulating layer being in contact with the top surface of thefirst electrode is defined by a first surface and a surface of theinsulating layer being in contact with a portion of the photoelectricconversion layer facing the charge storage electrode is defined by asecond surface, a side surface of the opening portion has a slopeexpanding from the first surface toward the second surface. Furthermore,the imaging element or the like may be configured to have a form wherethe side surface of the opening portion having the slope expanding fromthe first surface toward the second surface is located in a chargestorage electrode side. In addition, the above-described form includes aform where another layer is formed between the photoelectric conversionlayer and the first electrode (for example, a form where a materiallayer suitable for charge storage is formed between the photoelectricconversion layer and the first electrode).

Furthermore, in the imaging element or the like according to anembodiment of the present disclosure including various exemplary formsand configurations described above, the imaging element or the like mayhave a configuration where the imaging element further includes acontrol unit which is provided to the semiconductor substrate and has adriving circuit, the first electrode and the charge storage electrodeare connected to the driving circuit, in a charge storage period, fromthe driving circuit, a potential V₁₁ is applied to the first electrode,and a potential V₁₂ is applied to the charge storage electrode, so thatcharges are stored in the photoelectric conversion layer, and in acharge transfer period, from the driving circuit, a potential V₂₁ isapplied to the first electrode, and a potential V₂₂ is applied to thecharge storage electrode, so that the charges stored in thephotoelectric conversion layer are read out to the control unit throughthe first electrode. Herein, in the case where the potential of thefirst electrode is higher than the potential of the second electrode,

V₁₂≥V₁₁ and V₂₂<V₂₁, and

in the case where the potential of the first electrode is lower than thepotential of the second electrode,

V₁₂≤V₁₁ and V₂₂>V₂₁.

Furthermore, in the imaging element or the like according to anembodiment of the present disclosure including various exemplary formsand configurations described above, the imaging element or the like maybe configured to have a form where a transfer control electrode (chargetransfer electrode), which is arranged between the first electrode andthe charge storage electrode can be separated from the first electrodeand the charge storage electrode and is arranged to face thephotoelectric conversion layer through the insulating layer, is furtherincluded. Note that the imaging element or the like according to anembodiment of the present disclosure having such a form is, for theconvenience of description, referred to as an “imaging element or thelike according to an embodiment of the present disclosure having atransfer control electrode.”

In addition, in the imaging element or the like according to anembodiment of the present disclosure having a transfer controlelectrode, the imaging element or the like may have a configurationwhere a control unit, which is provided to a semiconductor substrate andincludes a driving circuit, is included, the first electrode, the chargestorage electrode, and the transfer control electrode are connected tothe driving circuit, in a charge storage period. From the drivingcircuit, a potential V₁₁ is applied to the first electrode, a potentialV₁₂ is applied to the charge storage electrode, and a potential V₁₃ isapplied to the transfer control electrode, so that charges are stored inthe photoelectric conversion layer. And, in a charge transfer period,from the driving circuit a potential V₂₁ is applied to the firstelectrode, a potential V₂₂ is applied to the charge storage electrode,and a potential V₂₃ is applied to the transfer control electrode, sothat the charges stored in the photoelectric conversion layer are readout to the control unit through the first electrode. Herein, in the casewhere a potential of the first electrode is higher than a potential ofthe second electrode,

V₁₂>V₁₃ and V₂₂≤V₂₃≤V₂₁, and

in the case where the potential of the first electrode is lower than thepotential of the second electrode,

V₁₂<V₁₃ and V₂₂≥V₂₃≥V₂₁.

Furthermore, in the imaging element or the like according to anembodiment of the present disclosure including various exemplary formsand configurations described above, the imaging element or the like maybe configured to have a form where a charge ejection electrode, which isconnected to the photoelectric conversion layer and is arranged to beseparated from the first electrode and the charge storage electrode, isfurther included. Note that the imaging element or the like according toan embodiment of the present disclosure having such a form is, for theconvenience of description, referred to as an “imaging element or thelike according to an embodiment of the present disclosure having acharge ejection electrode.” Furthermore, in the imaging element or thelike according to an embodiment of the present disclosure having acharge ejection electrode, the imaging element or the like may beconfigured to have a form where the charge ejection electrode isarranged to surround the first electrode and the charge storageelectrode (namely, in a frame shape). The charge ejection electrode maybe shared (commonly used) by a plurality of the imaging elements.Furthermore, in this case, the imaging element may be configured in aform where the photoelectric conversion layer extends in a secondopening portion provided to the insulating layer to be connected to thecharge ejection electrode, an edge of a top surface of the chargeejection electrode is covered with the insulating layer, the chargeejection electrode is exposed to a bottom surface of the second openingportion, and when a surface of the insulating layer being in contactwith the top surface of the charge ejection electrode is defined by athird surface and a surface of the insulating layer being in contactwith a portion of the photoelectric conversion layer facing the chargestorage electrode is defined by a second surface, and a side surface ofthe second opening portion has a slope expending from the third surfacetoward the second surface.

Furthermore, in the imaging element or the like according to anembodiment of the present disclosure having a charge ejection electrode,the imaging element or the like may have a configuration where a controlunit, which is provided to a semiconductor substrate and includes adriving circuit, is further included, the first electrode, the chargestorage electrode, and the charge ejection electrode are connected tothe driving circuit, in a charge storage period, from the drivingcircuit, a potential V₁₁ is applied to the first electrode, a potentialV₁₂ is applied to the charge storage electrode, and a potential V₁₄ isapplied to the charge ejection electrode, so that charges are stored inthe photoelectric conversion layer. And, in a charge transfer period,from the driving circuit a potential V₂₁ is applied to the firstelectrode, a potential V₂₂ is applied to the charge storage electrode,and a potential V₂₄ is applied to the charge ejection electrode, so thatthe charges stored in the photoelectric conversion layer are read out tothe control unit through the first electrode. Herein, in the case wherea potential of the first electrode is higher than a potential of thesecond electrode,

V₁₄>V₁₁ and V₂₄<V₂₁, and

in the case where the potential of the first electrode is lower than thepotential of the second electrode,

V₁₄<V₁₁ and V₂₄>V₂₁.

Furthermore, in the imaging element or the like according to anembodiment of the present disclosure including various exemplary formsand configurations described above, the imaging element or the like maybe configured in a form where the charge storage electrode is configuredwith a plurality of charge storage electrode segments. Note that theimaging element or the like according to an embodiment of the presentdisclosure having such a form is, for the convenience of description,referred to as an “imaging element or the like according to anembodiment of the present disclosure having a plurality of chargestorage electrode segments.” The number of charge storage electrodesegments may be two or more. Furthermore, in the imaging element or thelike according to an embodiment of the present disclosure having aplurality of charge storage electrode segments, the imaging element orthe like may be configured to have a form such that in the case where apotential of the first electrode is higher than a potential of thesecond electrode, in a charge transfer period, a potential applied tothe charge storage electrode segment located at the position closest tothe first electrode is higher than a potential applied to the chargestorage electrode segment located at the position farthest from thefirst electrode. And, in the case where the potential of the firstelectrode is lower than the potential of the second electrode, in thecharge transfer period, the potential applied to the charge storageelectrode segment located at the position closest to the first electrodeis lower than the potential applied to the charge storage electrodesegment located at the position farthest from the first electrode.

In the imaging element or the like according to an embodiment of thepresent disclosure including various exemplary forms and configurationsdescribed above, the imaging element or the like may have aconfiguration where at least a floating diffusion layer and anamplification transistor constituting a control unit are provided to asemiconductor substrate, and the first electrode is connected to thefloating diffusion layer and a gate portion of the amplificationtransistor, in this case, a reset transistor and a selection transistorconstituting the control unit are further provided to the semiconductorsubstrate, the floating diffusion layer is connected to one source/drainregion of the reset transistor, and one source/drain region of theamplification transistor is connected to one source/drain region of theselection transistor, and the other source/drain region of the selectiontransistor is connected to a signal line.

Furthermore, in the imaging element or the like according to anembodiment of the present disclosure including various exemplary formsand configurations described above, the imaging element or the like maybe configured to have a form where the charge storage electrode islarger than the first electrode. When the area of the charge storageelectrode is denoted by S₁ and the area of the first electrode isdenoted by S_(l), although it is not limited thereto, it is preferablethat the following relationship is satisfied.

4≤S ₁ ′/S ₁

Furthermore, in the imaging element or the like according to anembodiment of the present disclosure including various exemplary formsand configurations described above, the imaging element or the like maybe configured to have a form where light is incident from a secondelectrode side, and a light-shielding layer is formed in a lightincidence side of the second electrode. Alternatively, the imagingelement or the like may be configured to have a form where light isincident from a second electrode side, light is not incident on thefirst electrode (in some cases, the first electrode and the transfercontrol electrode). In this case, the imaging element or the like mayhave a configuration where a light-shielding layer is formed above thefirst electrode (in some cases, the first electrode and the transfercontrol electrode) as a light incidence side of the second electrode.The imaging element or the like may have a configuration where anon-chip microlens is provided above the charge storage electrode and thesecond electrode, and light incident on the on-chip microlens iscollected in the charge storage electrode. The light-shielding layer maybe arranged above the light-incident side surface of the secondelectrode or may be arranged on the light-incident side surface of thesecond electrode. In some cases, the light-shielding layer may be formedin the second electrode. As a material constituting the light-shieldinglayer, there may be exemplified chromium (Cr), copper (Cu), aluminum(Al), tungsten (W), and a resin which does not transmit light (forexample, polyimide resin).

As an imaging element according to an embodiment of the presentdisclosure, specifically, there may be exemplified an imaging element(for the convenience of description, referred to as a “first-type blueimaging element”) being sensitive to blue and including a photoelectricconversion layer (for the convenience of description, referred to as a“first-type blue photoelectric conversion layer”) absorbing blue light(light having a wavelength range of 425 nm to 495 nm), an imagingelement (for the convenience of description, referred to as a“first-type green imaging element”) being sensitive to green andincluding a photoelectric conversion layer (for the convenience ofdescription, referred to as a “first-type green photoelectric conversionlayer”) absorbing green light (light having a wavelength range of 495 nmto 570 nm), and an imaging element (for the convenience of description,referred to as a “first-type red imaging element”) being sensitive tored and including a photoelectric conversion layer (for the convenienceof description, referred to as a “first-type red photoelectricconversion layer”) absorbing red light (light having a wavelength rangeof 620 nm to 750 nm). In addition, as imaging elements having no chargestorage electrode in the related art, an imaging element being sensitiveto blue is, for the convenience of description, referred to as a“second-type blue imaging element;” an imaging element being sensitiveto green is, for the convenience of description, referred to as a“second-type green imaging element;” an imaging element being sensitiveto red is, for the convenience of description, referred to as a“second-type red imaging element;” a photoelectric conversion layerconstituting the second-type blue imaging element is, for theconvenience of description, referred to as a “second-type bluephotoelectric conversion layer;” a photoelectric conversion layerconstituting the second-type green imaging element is, for theconvenience of description, referred to as a “second-type greenphotoelectric conversion layer;” and a photoelectric conversion layerconstituting the second-type red imaging element is, for the convenienceof description, referred to as a “second-type red photoelectricconversion layer.”

The stacked-type imaging element according to an embodiment of thepresent disclosure includes at least one imaging element (photoelectricconversion element) according to an embodiment of the presentdisclosure. That is, the stacked-type imaging element may include, butis not limited to, the following non-limiting configurations andstructures.

(A) A configuration and structure where the first-type bluephotoelectric conversion unit, the first-type green photoelectricconversion unit, and the first-type red photoelectric conversion unitare stacked in the vertical direction, and

the respective control units for the first-type blue imaging element,the first-type green imaging element, and the first-type red imagingelement are provided in the semiconductor substrate.

(B) A configuration and structure where the first-type bluephotoelectric conversion unit and the first-type green photoelectricconversion unit are stacked in the vertical direction,

the second-type red photoelectric conversion unit is arranged below thetwo first-type photoelectric conversion units, and

the respective control units for the first-type blue imaging element,the first-type green imaging element, and the second-type red imagingelement are provided in the semiconductor substrate.

(C) A configuration and structure where the second-type bluephotoelectric conversion unit and the second-type red photoelectricconversion unit are arranged below the first-type green photoelectricconversion unit, and

the respective control units for the first-type green imaging element,the second-type blue imaging element, and the second-type red imagingelement are provided in the semiconductor substrate

(D) A configuration and structure where the second-type greenphotoelectric conversion unit and the second-type red photoelectricconversion unit are arranged below the first-type blue photoelectricconversion unit, and

the respective control units for the first-type blue imaging element,the second-type green imaging element, and the second-type red imagingelement are provided in the semiconductor substrate. Note that it ispreferable that the arrangement order of the photoelectric conversionunits of the imaging element in the vertical direction is an order ofthe blue photoelectric conversion unit, the green photoelectricconversion unit, and the red photoelectric conversion unit from thelight-incident direction or an order of the green photoelectricconversion unit, the blue photoelectric conversion unit, and the redphotoelectric conversion unit from the light-incident direction. This isbecause light having a shorter wavelength is absorbed in the incidentsurface side more efficiently. Since red light has the longestwavelength among three colors of light, it is preferable that the redphotoelectric conversion unit is located in the lowest layer as viewedfrom the light-incident surface. One pixel is configured in the stackedstructure of the imaging element. A first-type infrared-rayphotoelectric conversion unit may also be included. Herein, it ispreferable that a photoelectric conversion layer of the first-typeinfrared-ray photoelectric conversion unit is configured with, forexample, an organic material, and the photoelectric conversion layer islocated in the lowest layer of the stacked structure of the first-typeimaging element and is arranged above the second-type imaging element.In addition, a second-type infrared-ray photoelectric conversion unitmay also be included below the first-type photoelectric conversion unit.

In the first-type imaging element, for example, the first electrode isformed on an interlayer insulating layer provided on the semiconductorsubstrate. The imaging element formed in the semiconductor substrate maybe configured to be of a back-illuminated type or of a front-illuminatedtype.

In the case where the photoelectric conversion layer is made of anorganic material, the photoelectric conversion layer may be formed inany one of the following non-limiting forms:

(1) The photoelectric conversion layer is configured with a p-typeorganic semiconductor;

(2) The photoelectric conversion layer is configured with an n-typeorganic semiconductor;

(3) The photoelectric conversion layer is configured with a stackedstructure of a p-type organic semiconductor layer/an n-type organicsemiconductor layer; (for example, the photoelectric conversion layer isconfigured with a stacked structure of a p-type organic semiconductorlayer/a mixed layer (bulk hetero structure) of a p-type organicsemiconductor and an n-type organic semiconductor/an n-type organicsemiconductor layer. The photoelectric conversion layer is configuredwith a stacked structure of a p-type organic semiconductor layer/a mixedlayer (bulk hetero structure) of a p-type organic semiconductor and ann-type organic semiconductor. The photoelectric conversion layer isconfigured with a stacked structure of an n-type organic semiconductorlayer/a mixed layer (bulk hetero structure) of a p-type organicsemiconductor and an n-type organic semiconductor.)

(4) The photoelectric conversion layer is configured with a mixed layer(bulk hetero structure) of a p-type organic semiconductor and an n-typeorganic semiconductor.

Herein, the stack order may be configured to be arbitrarily changed.

As a p-type organic semiconductor, one or more of the followingnon-limiting materials may be used: naphthalene derivatives, anthracenederivatives, phenanthrene derivatives, pyrene derivatives, perylenederivatives, tetracene derivatives, pentacene derivatives, quinacridonederivatives, thiophene derivatives, thieno thiophene derivatives,benzothiophene derivatives, benzo-thieno benzothiophene derivatives,triallyl amine derivatives, carbazole derivatives, perylene derivatives,picene derivatives, chrysene derivatives, fluoranthene derivatives,phthalocyanine derivatives, subphthalocyanine derivatives,subporphyrazine derivatives, metal complexes having heterocycliccompounds as ligands, polythiophene derivatives, poly benzothiadiazolederivatives, polyfluorene derivatives, and the like. As an n-typeorganic semiconductor, one or more of the following non-limitingmaterials may be used: fullerene and fullerene derivatives <for example,fullerenes (higher-order fullerenes) such as C60, C70, and C74,endohedral fullerenes, or the like, or fullerene derivatives (forexample, fullerene fluorides, PCBM fullerene compounds, fullerenemultimers, or the like)>, organic semiconductors having HOMO and LUMOlarger (deeper) than that of p-type organic semiconductors, andtransparent inorganic metal oxides. An n-type organic semiconductor mayinclude, but is not limited to, one or more of organic molecules ororganometallic complexes having, as a portion of the molecular skeleton,heterocyclic compounds containing nitrogen atoms, oxygen atoms, orsulfur atoms, for example, pyridine derivatives, pyrazine derivatives,pyrimidine derivatives, triazine derivatives, quinoline derivatives,quinoxaline derivatives, isoquinoline derivatives, acridine derivatives,phenazine derivatives, phenanthroline derivatives, tetrazolederivatives, pyrazole derivatives, imidazole derivatives, thiazolederivatives, oxazole derivatives, imidazole derivatives, benzimidazolederivatives, benzotriazole derivatives, benzoxazole derivatives,benzoxazole derivatives, carbazole derivatives, benzofuran derivatives,dibenzofuran derivatives, subporphyrazine derivatives,polyphenylenevinylene derivatives, poly benzothiadiazole derivatives,polyfluorene derivatives, or the like, and subphthalocyaninederivatives. A group or the like contained in the fullerene derivativesmay include, but is not limited to one or more of halogen atoms;straight-chained, branched, or cyclic alkyl groups or phenyl groups;groups having a straight-chained or condensed-cyclic aromatic compound;groups having a halide; partial fluoroalkyl groups; perfluoroalkylgroups; silylalkyl groups; silylalkoxy groups; arylsilyl groups;arylsulfanyl groups; alkylsulfanyl groups; arylsulfonyl groups;alkylsulfonyl groups; arylsulfide groups; alkylsulfide groups; aminogroups; alkylamino groups; arylamino groups; hydroxy groups; alkoxygroups; acylamino groups; acyloxy groups; carbonyl groups; carboxygroups; carboxymethyl kiso amide groups; carboalkoxy groups; acylgroups; sulfonyl groups; cyano groups; nitro groups; groups having achalcogenide; phosphine groups; phosphonate groups; and derivativesthereof. A thickness of the photoelectric conversion layer (in somecases, referred to as an “organic photoelectric conversion layer”)configured with an organic material, although it is not limited thereto,may include the following non-limiting range of 1×10⁻⁸ m to 5×10⁻⁷ m,preferably a range of 2.5×10⁻⁸ m to 3×10⁻⁷ m, more preferably a range of2.5×10⁻⁸ m to 2×10⁻⁷ m, and much more preferably a range of 1×10⁻⁷ m to1.8×10⁻⁷ m. Note that, in many cases, organic semiconductors areclassified into a p type and an n type. Herein, the p type denotes thatholes may be easy to transport, and the n type denotes that electronsmay be easy to transport. The types are not restrictively interpreted.

A material constituting an organic photoelectric conversion layer forphotoelectrically converting light having a green wavelength, mayinclude but is not limited to one or more of: rhodamine-based dyes,merashianin-based dyes, quinacridone derivatives, subphthalocyanine dyes(subphthalocyanine derivative), and the like. A material constituting anorganic photoelectric conversion layer for photoelectrically convertinglight having a blue wavelength, may include, but is not limited to oneor more of: coumarin acid dyes, tris-8-hydroxyquinoline aluminum (Alq3),merashianin-based dyes, and the like. A material of an organicphotoelectric conversion layer for photoelectrically converting lighthaving a red wavelength, may include, but is not limited to one or moreof phthalocyanine dyes, subphthalocyanine dyes (subphthalocyaninederivatives), and the like.

An inorganic material of the photoelectric conversion layer, mayinclude, but is not limited to, one or more of compound semiconductorsof crystalline silicon, amorphous silicon, microcrystalline silicon,crystalline selenium, amorphous selenium, a chalcopyrite-based compoundsuch as CIGS (CuInGaSe), CIS (CuInSe₂), CuInS₂, CuAlS₂, CuAlSe₂, CuGaS₂,CuGaSe₂, AgAlS₂, AgAlSe₂, AgInS₂, or AgInSe₂, a group III-V compoundsuch as GaAs, InP, AlGaAs, InGaP, AlGaInP, or InGaAsP, CdSe, CdS,In₂Se₃, In₂S₃, Bi₂Se₃, Bi₂S₃, ZnSe, ZnS, PbSe, and PbS. Quantum dotsmade of these materials may be used for the photoelectric conversionlayer.

Alternatively, the photoelectric conversion layer may be configured tohave a stacked layer structure of a lower semiconductor layer and anupper photoelectric conversion layer. In this manner, by providing thelower semiconductor layer, it is possible to prevent recoupling in thecharge storage period, so that it is possible to increase transferefficiency of the charges stored in the photoelectric conversion layerto the first electrode, and it is possible to suppress the occurrence ofdark current. The materials constituting the upper layer photoelectricconversion layer may be appropriately selected among various types ofmaterials constituting the photoelectric conversion layer describedabove. On the other hand, it is preferable that, as the materialsconstituting the lower semiconductor layer, a material having a largeband gap energy value (for example, a band gap energy value of 3.0 eV ormore) and having a mobility higher than those of the materialsconstituting the photoelectric conversion layer is used. Specifically,non-limiting examples of the material may include one or more of oxidesemiconductor materials such as IGZO; transition metal diechalcogenides; silicon carbides; diamond; graphene; carbon nanotubes;and organic semiconductor materials of condensed polycyclic hydrocarboncompounds, condensed heterocyclic compounds, or the like. As materialsconstituting the lower semiconductor layer, in the case where theto-be-stored charges are holes, example materials include, but are notlimited to, materials having an ionization potential lower than theionization potential of the materials constituting the photoelectricconversion layer; and in the case where the to-be-stored charges areelectrons, example materials include, but are not limited to materialshaving an electron affinity larger than the electron affinity of thematerials constituting the photoelectric conversion layer. It ispreferable that impurity concentration in the materials constituting thelower semiconductor layer is 1×10¹⁸ cm⁻³ or less. The lowersemiconductor layer may have a single layer configuration or may be amulti-layer configuration. In addition, the materials constituting thelower semiconductor layer located above the charge storage electrode andthe materials constituting the lower semiconductor layer located abovethe first electrode may be configured to be different from each other.

According to the solid-state imaging device in the first or secondembodiments of the present disclosure, a single-plate color solid-stateimaging device may be configured.

In the solid-state imaging device according to the second embodiment ofthe present disclosure having a stacked-type imaging element, unlike asolid-state imaging device having imaging elements in a Bayer array(namely, not performing spectral separation of blue light, green light,and red light by using color filters), one pixel is configured bystacking imaging elements being sensitive to light having plural typesof wavelength in the light-incident direction in the same pixel, it ispossible to improve sensitivity and pixel density per unit volume. Inaddition, since an organic material has a high absorption coefficient,the organic photoelectric conversion layer can be configured to have asmaller thickness than a Si-based photoelectric conversion layer of therelated art, and light leakage from adjacent pixels or limitation of alight-incident angle is alleviated. Furthermore, in Si-based imagingelements of the related art, an interpolation process among three colorpixels is performed, so that false color occurs in order to generate acolor signal. However, in the solid-state imaging device according tothe second embodiment of the present disclosure having a stacked-typeimaging element, the occurrence of false color is suppressed. Since theorganic photoelectric conversion layer itself has a function as a colorfilter, color separation can be obtained without arrangement of colorfilters.

On the other hand, in the solid-state imaging device according to thefirst embodiment of the present disclosure where color filters are used,requirements for spectral separation characteristics for blue light,green light, and red light can be alleviated, and a high productivitycan be obtained. An array of the imaging element in the solid-stateimaging device according to the first embodiment of the presentdisclosure, includes, but is not limited to, one or more of a Bayerarray, an interline arrangement, a G stripe RB checkered array, a Gstripe RB completely checkered array, a checkered complementary colorarray, a stripe array, a diagonal stripe arrangement, a primary colordifference array, a field color difference sequential array, a framecolor difference sequential array, a MOS-type array, an improvedMOS-type array, a frame interleaved array, and a field interleavedarray. Herein, one pixel (or subpixel) is configured with one imagingelement.

A pixel region where a plurality of the imaging elements according to anembodiment of the present disclosure or a plurality of the stacked-typeimaging elements according to an embodiment of the present disclosureare arranged is configured with a plurality of pixels which areregularly arranged in a two-dimensional array shape. The pixel region istypically configured to include an effective pixel region of actuallyreceiving light, amplifying signal charges generated throughphotoelectric conversion, and reading out the signal charges to adriving circuit and a black reference pixel region for outputtingoptical black as a reference of a black level. The black reference pixelregion is typically arranged in the outer periphery of the effectivepixel region.

In the imaging element or the like according to an embodiment of thepresent disclosure including various exemplary forms and configurationsdescribed above, light is illuminated, and photoelectric conversionoccurs in the photoelectric conversion layer, so that holes andelectrons are separated as carriers. Then, the electrode where the holesare extracted is defined as an anode, the electrode where the electronsare extracted is defined as a cathode. There may be a form where thefirst electrode constitutes the anode, and the second electrodeconstitutes the cathode. On the contrary, there may also be a form wherethe first electrode constitutes the cathode, and the second electrodeconstitutes the anode.

In the case of constituting the stacked-type imaging element, the firstelectrode, the charge storage electrode, the transfer control electrode,the charge ejection electrode, and the second electrode may beconfigured to be made of a transparent conductive material. Note that,in some cases, the first electrode, the charge storage electrode, thetransfer control electrode, and the charge ejection electrode arecollectively referred to as a “first electrode or the like.”Alternatively, in the case where the imaging elements according to anembodiment of the present disclosure or the like are arranged in aplane, for example, like in a Bayer array, the second electrode may beconfigured to be made of a transparent conductive material, and thefirst electrode may be configured to be made of a metal material. Inthis case, specifically, the second electrode located at thelight-incident side may be configured to be made of a transparentconductive material, and the first electrode and the like may beconfigured to be made of, for example, Al—Nd (alloy of aluminum andneodymium) or ASC (alloy of aluminum, samarium, and copper). Note that,in some cases, an electrode made of a transparent conductive material isreferred to as a “transparent electrode.” The band gap energy of thetransparent conductive material is 2.5 eV or, more preferably, 3.1 eV orgreater. As a transparent conductive material constituting thetransparent electrode, there may be exemplified a conductive metaloxide; the conductive oxide may include, but is not limited to, one ormore of an indium oxide, an indium tin oxide (ITO, Sn-doped In₂O₃,including a crystalline ITO and an amorphous ITO), an indium zinc oxide(IZO) formed by adding indium as a dopant to a zinc oxide, an Indiumgallium oxide (IGO) formed by adding indium as a dopant to a galliumoxide, an indium gallium zinc oxide (IGZO, In-GaZnO₄) formed by addingindium and gallium as dopants to a zinc oxide, an indium tin zinc oxide(ITZO) formed by adding tin as a dopant to a zinc oxide, an IFO (F-dopedIn₂O₃), a tin oxide (SnO₂), an ATO (Sb-doped SnO₂), an FTO (F-dopedSnO₂), a zinc oxide (including ZnO doped with another elements), analuminum zinc oxide (AZO) formed by adding aluminum as a dopant to azinc oxide, a gallium zinc oxide (GZO) formed by adding gallium as adopant to a zinc oxide, a titanium oxide (TiO₂), a niobium titaniumoxide (TNO) formed by adding niobium as a dopant to a titanium oxide, anantimony oxide, a spinel-type oxide, and an oxide having a YbFe₂O₄structure. Alternatively, a transparent electrode using one or more of agallium oxide, a titanium oxide, a niobium oxide, a nickel oxide, or thelike as a mother layer may be exemplified. As a thickness of thetransparent electrode, an example of a non-limiting range may be 2×10⁻⁸m to 2×10⁻⁷ m, preferably, a range of 3×10⁻⁸ m to 1×10⁻⁷ m. In the casewhere transparency is necessary for the first electrode, from the pointview of simplification of the manufacturing process, it is preferablethat the charge ejection electrode is also made of a transparentconductive material.

In the case where transparency is not necessary, it is preferable that aconductive material constituting a positive electrode having a functionas an electrode of ejecting holes is a conductive material having a highwork function (for example, φ=4.5 eV to 5.5 eV)). Specifically, theconductive material may include, but is not limited to, one or more ofgold (Au), silver (Ag), chromium (Cr), nickel (Ni), palladium (Pd),platinum (Pt), iron (Fe), iridium (Ir), germanium (Ge), osmium (Os),rhenium (Re), or tellurium (Te). On the other hand, it is preferablethat a conductive material constituting a negative electrode having afunction as an electrode of ejecting electrons is a conductive materialhaving a low work function (for example, φ=3.5 eV to 4.5 eV).Specifically, the conductive material may include, but is not limited toone or more of an alkali metal (for example Li, Na, K, or the like) anda fluoride thereof or an oxide thereof, an alkaline earth metal (forexample, Mg, Ca, or the like) and a fluoride thereof or an oxidethereof, aluminum (Al), zinc (Zn), tin (Sn), thallium (Tl), a sodiumpotassium alloy, an aluminum lithium alloy, a magnesium silver alloy,indium, a rare earth metal such as ytterbium, or alloys thereof.Materials constituting the anode or the cathode include, but are notlimited to one or more metals such as platinum (Pt), gold (Au),palladium (Pd), chromium (Cr), nickel (Ni), aluminum (Al), silver (Ag),tantalum (Ta), tungsten (W), copper (Cu), titanium (Ti), indium (In),tin (Sn), iron (Fe), cobalt (Co), and molybdenum (Mo), alloys containingthese metal atoms, conductive particles made of these metals, conductiveparticles of alloys containing these metals, or conductive materialssuch as polysilicon containing impurities, carbon-based materials, oxidesemiconductors, carbon nano tubes, and graphene, and a stacked structureof layers containing these atoms may be used. Furthermore, materialsconstituting the anode or the cathode include but are not limited to oneor more of an organic material (conductive polymer) such aspoly(3,4-ethylenedioxythiophene)/polystyrene sulfonic acid (PEDOT/PSS).In addition, a cured material of a paste or ink obtained by mixing theconductive material with a binder (polymer) may be used as an electrode.

As a film formation method for the first electrode or the like or thesecond electrode (an anode or a cathode), a dry method or a wet methodmay be used. Examples of a dry method include, but are not limited to aphysical vapor deposition (PVD) method and a chemical vapor deposition(CVD) method. Examples of a film forming method using the principle ofthe PVD method, include but are not limited to, a vacuum vapordeposition method using resistance heating or high-frequency heating, anEB (electron beam) vapor deposition method, various sputtering methods(a magnetron sputtering method, an RF-DC coupling type bias sputteringmethod, an ECR sputtering method, a facing target sputtering method, anda high-frequency sputtering method), an ion plating method, a laserablation method, a molecular beam epitaxy method, and a laser transfermethod. In addition, examples of a CVD method include, but are notlimited to, a plasma CVD method, a thermal CVD method, a metalorganic(MO) CVD method, and a photo CVD method. On the other hand, examples ofa wet method, include but are not limited to an electrolytic platingmethod or an electroless plating method, a spin coating method, anink-jet method, a spray coating method, a stamp method, a micro-contactprinting method, a flexographic printing method, an offset printingmethod, a gravure printing method, a dip method, and the like. Examplesof a patterning method, include but are not limited to chemical etchingsuch as shadow mask, laser transfer, or photolithography and physicaletching using ultraviolet light, laser, or the like. Planarizationtechniques for the first electrode or the like or the second electrodemay include but are not limited to, a laser planarization method, areflow method, a chemical mechanical polishing (CMP) method, and thelike.

The insulating layer may include one or more of the followingnon-limiting materials: besides inorganic insulating materialsexemplified as metal oxide high dielectric insulating materials such asa silicon oxide-based material; a silicon nitride (SiN_(y)); and analuminum oxide (Al₂O₃), such as polymethyl methacrylate (PMMA);polyvinyl phenol (PVP); polyvinyl alcohol (PVA); polyimide;polycarbonate (PC); polyethylene terephthalate (PET); polystyrene; asilanol derivative (silane coupling agent such as N-2 (aminoethyl)3-aminopropyltrimethoxysilane (AEAPTMS), 3-mercaptopropyltrimethoxysilane (MPTMS), or octadecyltrichlorosilane (OTS); novolaktype phenolic resin; a fluorine-based resin; and organic insulatingmaterials (organic polymers) exemplified as a straight-chain hydrocarbonhaving, in one end thereof, a functional group capable of being bound toa control electrode such as octadecanethiol or dodecyl isocyanate, and acombination thereof may be used. Note that, as a silicon oxide-basedmaterial, non-limiting examples include, but are not limited to, asilicon oxide (SiO_(x)), BPSG, PSG, BSG, AsSG, PbSG, a siliconoxynitride (SiON), a SOG (spin-on-glass), and a low-dielectric constantmaterial (for example, polyaryl ether, cyclo perfluorocarbon polymer andbenzocyclobutene, a cyclic fluorine resin, polytetrafluoroethylene, anaryl ether fluoride, a polyimide fluoride, an amorphous carbon, and anorganic SOG). Materials constituting various interlayer insulatinglayers or insulating films may also be appropriately selected from theaforementioned materials.

The configuration and structure of the floating diffusion layer, theamplification transistor, the reset transistor, and the selectiontransistor constituting the control unit may be formed to be similar tothe configuration and structure of the floating diffusion layer, theamplification transistor, the reset transistor, and the selectiontransistor in the related art. The driving circuit may also be formedwith a well-known configuration and structure.

The first electrode is connected to the floating diffusion layer and thegate portion of the amplification transistor, and thus, it is desirablethat contact hole portions are formed for the connection between thefirst electrode and the floating diffusion layer and between the firstelectrode and the gate portion of the amplification transistor. Thematerial constituting the contact hole portion may include, but is notlimited to one or more of the following: polysilicon doped withimpurities, a high-melting-point metal or metal silicide such astungsten, Ti, Pt, Pd, Cu, TiW, TiN, TiNW, WSi₂, and MoSi₂, and a stackedstructure (for example, Ti/TiN/W) of layers made of these materials.

A first carrier blocking layer may be provided between the organicphotoelectric conversion layer and the first electrode, and a secondcarrier blocking layer may be provided between the organic photoelectricconversion layer and the second electrode. In addition, a first chargeinjection layer may be provided between the first carrier blocking layerand the first electrode, and a second charge injection layer may beprovided between the second carrier blocking layer and the secondelectrode. The material constituting the electrode injection layer mayinclude but is not limited to one or more of the following: alkalimetals such as lithium (Li), sodium (Na), and potassium (K), fluoridesthereof, oxides thereof, alkaline earth metals such as magnesium (Mg)and calcium (Ca) fluorides thereof, and oxides thereof.

A method for forming various organic layers may include, but is notlimited to one or more of the following: a dry film formation method anda wet film formation method. An example of a dry film formation method,includes but is not limited to one or more of the following: aresistance heating or high-frequency heating method, a vacuum vapordeposition method using electron beam heating, a flash vapor depositionmethod, a plasma vapor deposition method, an EB vapor deposition method,various sputtering methods (a 2-pole sputtering method, a DC sputteringmethod, a DC magnetron sputtering method, a high-frequency sputteringmethod, a magnetron sputtering method, an RF-DC coupling type biassputtering method, an ECR sputtering method, a facing target sputteringmethod, a high-frequency sputtering method, and an ion beam sputtering),a direct current (DC) method, an RF method, a multi-cathode method, anactivation reaction method, an electric field vapor deposition method,various ion plating methods such as a high-frequency ion plating methodand a reactive ion plating method, a laser ablation method, a molecularbeam epitaxy method, a laser transfer method, and a molecular beamepitaxy (MBE) method. In addition, an example of a CVD method includesbut is not limited to, a plasma CVD method, a thermal CVD method, anMOCVD method, and a photo-CVD method. On the other hand, examples of awet method include, but are not limited to, a spin coating method; animmersion method; a casting method; a micro-contact printing method; adrop-casting method; various printing methods such as a screen printingmethod, an inkjet printing method, an offset printing method, a gravureprinting method, and a flexographic printing method; a stamping method;a spray method; and various coating methods such as an air doctor coatermethod, a blade coater method, a rod coater method, a knife coatermethod, a squeeze coater method, a reverse roll coater method, atransfer roll coater method, a gravure coater method, a kiss coatermethod, a cast coater method, a spray coating method, a slit orificecoater method, and a calendar coater method. Note that, in the coatingmethods, a solvent including, but not limited to, organic solventshaving no polarity or low polarity such as toluene, chloroform, hexane,and ethanol may be used. An example of a patterning method includes, butis not limited to one or more of the following: chemical etching such asshadow mask, laser transfer, or photolithography and physical etchingusing ultraviolet light, laser, or the like. An example of aplanarization technique for various types of organic layers includes,but is not limited to one or more of the following: a laserplanarization method, a reflow method, and the like.

In the imaging element or the solid-state imaging device, as describedabove, if necessary, an on-chip microlens or a light-shielding layer maybe provided, and a driving circuit or a wire line for driving theimaging element is provided. If necessary, a shutter for controllingincidence of light on the imaging element may be provided, and thesolid-state imaging device may include an optical cut-off filteraccording to the purpose thereof.

For example, in the case where stacking a solid-state imaging device anda read-out integrated circuit (ROIC), a driving substrate where theread-out integrated circuit and a connection portion made of copper (Cu)are formed and the imaging element where a connection portion is formedare allowed to overlap with each other so that the connection portionsare in contact with each other, and then, the stacking is performed byadhering the connection portions. Alternatively, the connection portionsmay be adhered to each other by using solder bump or the like.

EXAMPLE 1

Example 1 relates to an imaging element according to an embodiment ofthe present disclosure, a stacked-type imaging element according to anembodiment of the present disclosure, and a solid-state imaging deviceaccording to a second embodiment of the present disclosure.

A schematic partial cross-sectional view of a portion of the imagingelement and the stacked-type imaging element of Example 1 is illustratedin FIG. 1A. Equivalent circuit diagrams of the imaging element and thestacked-type imaging element of Example 1 are illustrated in FIGS. 2 and3. A schematic layout view of the first electrode and the charge storageelectrode constituting the imaging element of Example 1 and transistorsconstituting a control unit is illustrated in FIG. 4. Potential statesof components in an operation period of the imaging element of Example 1are illustrated in FIG. 5. In addition, a schematic layout view of thefirst electrode and the charge storage electrode constituting theimaging element of Example 1 is illustrated in FIG. 6. A schematicperspective view of the first electrode, the charge storage electrode, asecond electrode, and a contact hole portion constituting the imagingelement of Example 1 is illustrated in FIG. 7. A conceptual diagram ofthe solid-state imaging device of Example 1 is illustrated in FIG. 8.

The imaging element (for example, the later-described green imagingelement) of Example 1 is configured to include a photoelectricconversion unit formed by stacking a first electrode 11, a photoelectricconversion layer 15, and a second electrode 16. The photoelectricconversion unit is configured to include a charge storage electrode 12,which is arranged to be separated from the first electrode 11 and isarranged to face the photoelectric conversion layer 15 with aninsulating layer 82 interposed therebetween.

As depicted in FIGS. 1B-D, the insulating layer 82 may include multiplelayers 82E and 82F. For example, a first region of the insulatingmaterial 82 between the charge storage electrode 12 and thephotoelectric conversion layer 15 may exist, and a second region of theinsulating material 82 between the charge storage electrode 12 and thefirst electrode 11 may exist. In some embodiments, the second region ofthe insulating material includes a first insulating layer 82E includingthe insulating material and a second insulating layer 82F including theinsulating material, and the first insulating material 82F is stacked onthe second insulating material 82E. FIGS. 1B-D further depict variousconfigurations with respect to the insulating layer 82 (e.g., theconfigurations of layers 82E and 82F change).

In addition, the stacked-type imaging element of Example 1 includes atleast one imaging element of Example 1. In Example 1, the stacked-typeimaging element includes one imaging element of Example 1.

Furthermore, the solid-state imaging device of Example 1 includes aplurality of the stacked-type imaging elements of Example 1.

Furthermore, a semiconductor substrate (more specifically, a siliconsemiconductor layer) 70 is further included, and the photoelectricconversion unit arranged above the semiconductor substrate 70. Inaddition, a control unit, which is provided in the semiconductorsubstrate 70 and has a driving circuit to which the first electrode 11is connected, is further included. Herein, the light-incident side ofthe semiconductor substrate 70 is set to “above the semiconductorsubstrate,” and the opposite side of the semiconductor substrate 70 isset to “below the semiconductor substrate.” A wire line layer 62configured with a plurality of wire lines is provided below thesemiconductor substrate 70. The semiconductor substrate 70 is providedwith at least a floating diffusion layer FD₁ and an amplificationtransistor TR1 _(amp) constituting the control unit, and the firstelectrode 11 is connected to the floating diffusion layer FD₁ and thegate portion of the amplification transistor TR1 _(amp). Thesemiconductor substrate 70 is further provided with a reset transistorTR1 _(rst) and a selection transistor TR1 _(sel) constituting thecontrol unit. The floating diffusion layer FD₁ is connected to the onesource/drain region of the reset transistor TR1 _(rst), the onesource/drain region of the amplification transistor TR1 _(amp) isconnected to the one source/drain region of the selection transistor TR1_(sel), and the other source/drain region of the selection transistorTR1 _(sel) is connected to a signal line VSL₁. The amplificationtransistor TR1 _(amp), the reset transistor TR1 _(rst), and theselection transistor TR1 _(sel) constitute a driving circuit.

Specifically, the imaging element and the stacked-type imaging elementof Example 1 are a back-illuminated type imaging element and aback-illuminated type stacked-type imaging element and includes astacked structure of three imaging elements of a first-type greenimaging element of Example 1 (hereinafter, referred to as a “firstimaging element”) being sensitive to green and including a first-typegreen photoelectric conversion layer absorbing green light, asecond-type blue imaging element of the related art (hereinafter,referred to as a “second imaging element”) being sensitive to blue andincluding a second-type blue photoelectric conversion layer absorbingblue light, and a second-type red imaging element of the related art(hereinafter, referred to as a “third imaging element”) being sensitiveto red and including a second-type red photoelectric conversion layerabsorbing red light. The red imaging element (third imaging element) andthe blue imaging element (second imaging element) are provided in thesemiconductor substrate 70, and the second imaging element is located tobe closer to the light-incident side than the third imaging element. Inaddition, the green imaging element (first imaging element) is providedabove the blue imaging element (second imaging element). One pixel isconfigured in a stacked structure of the first imaging element, thesecond imaging element, and the third imaging element. No color filteris provided.

In the first imaging element, the first electrode 11 and the chargestorage electrode 12 are formed on an interlayer insulating layer 81 tobe separated from each other. The interlayer insulating layer 81 and thecharge storage electrode 12 are covered with the insulating layer 82.The photoelectric conversion layer 15 is formed on the insulating layer82, and the second electrode 16 is formed on the photoelectricconversion layer 15. In the entire surface, including the secondelectrode 16, a protective layer 83 is formed, and an on-chip microlens90 is provided on the protective layer 83. The first electrode 11, thecharge storage electrode 12, and the second electrode 16 are configuredwith transparent electrodes made of, for example, ITO. The photoelectricconversion layer 15 is configured with a layer containing a well-knownorganic photoelectric conversion material (for example, an organicmaterial such as, but not limited to, a rhodamine-based dye, amerashianin-based dye, and quinacridone) being sensitive to green. Inaddition, the photoelectric conversion layer 15 may further have aconfiguration including a material layer suitable for charge storage.Namely, the material layer suitable for charge storage may be formedbetween the photoelectric conversion layer 15 and the first electrode 11(for example, in the connection portion 67). The interlayer insulatinglayer 81, the insulating layer 82, and the protective layer 83 areconfigured with well-known insulating materials (for example, SiO₂ orSiN). The photoelectric conversion layer 15 and the first electrode 11are connected to each other by the connection portion 67 provided to theinsulating layer 82. The photoelectric conversion layer 15 extends inthe connection portion 67. Namely, the photoelectric conversion layer 15extends in an opening portion 84 provided to the insulating layer 82 tobe connected to the first electrode 11.

The charge storage electrode 12 is connected to the driving circuit.Specifically, the charge storage electrode 12 is connected to a verticaldriving circuit 112 constituting the driving unit through a connectionhole 66, a pad portion 64, and a wire line V_(OA) provided in theinterlayer insulating layer 81.

The charge storage electrode 12 is larger than the first electrode 11.When the area of the charge storage electrode 12 is denoted by S₁′ andthe area of the first electrode 11 is denoted by S₁, although it is notlimited thereto, it is preferable that the following relationship issatisfied,

4≤S ₁ ′/S ₁

and, in Example 1, although it is not limited thereto, for example, thefollowing relationship is set.

S ₁ ′/S ₁=8

An element isolation region 71 is formed in a first surface (frontsurface) 70A side of the semiconductor substrate 70, and an oxide film72 is formed on the first surface 70A of the semiconductor substrate 70.

Furthermore, the first surface side of the semiconductor substrate 70 isprovided with the reset transistor TR1 _(rst), the amplificationtransistor TR1 _(amp), and the selection transistor TR1 _(sel)constituting the control unit for the first imaging element and isfurther provided with the first floating diffusion layer FD₁.

The reset transistor TR1 _(rst) is configured with a gate portion 51, achannel forming region 51A, and source/drain regions 51B and 51C. Thegate portion 51 of the reset transistor TR1 _(rst) is connected to areset line RST₁, the one source/drain region 51C of the reset transistorTR1 _(rst) also serves as a first floating diffusion layer FD₁, and theother source/drain region 51B thereof is connected to a power sourceV_(DD).

The first electrode 11 is connected to the one source/drain region 51C(first floating diffusion layer FD₁) of the reset transistor TR1 _(rst)through a connection hole 65 and a pad portion 63 provided in theinterlayer insulating layer 81, a contact hole portion 61 provided tothe semiconductor substrate 70 and the interlayer insulating layer 76,and the wire line layer 62 formed in the interlayer insulating layer 76.

The amplification transistor TR1 _(amp) is configured with a gateportion 52, a channel forming region 52A, and source/drain regions 52Band 52C. The gate portion 52 is connected to the first electrode 11 andthe one source/drain region 51C (first floating diffusion layer FD₁) ofthe reset transistor TR1 _(rst) through the wire line layer 62. Inaddition, the one source/drain region 52C shares the regions with theother source/drain region 51B constituting the reset transistor TR1_(rst) and is connected to the power source V_(DD).

The selection transistor TR1 _(sel) is configured with a gate portion53, a channel forming region 53A, and source/drain regions 53B and 53C.The gate portion 53 is connected to the select line SEL₁. In addition,the one source/drain region 53B shares the region with the othersource/drain region 52C constituting the amplification transistor TR1_(amp), and the other source/drain region 53C is connected to the signalline (data output line) VSL₁ (117).

The second imaging element includes an n-type semiconductor region 41provided to the semiconductor substrate 70 as a photoelectric conversionlayer. A gate portion 45 of the transfer transistor TR2 _(trs)configured with a vertical-type transistor extends to the n-typesemiconductor region 41 and is connected to a transfer gate line TG₂. Inaddition, a second floating diffusion layer FD₂ is provided to a region45C of the semiconductor substrate 70 in the vicinity of the gateportion 45 of the transfer transistor TR2 _(trs). The charges stored inthe n-type semiconductor region 41 are read out to the second floatingdiffusion layer FD₂ through a transfer channel formed along the gateportion 45.

In the second imaging element, in the first surface side of thesemiconductor substrate 70, a reset transistor TR2 _(rst), anamplification transistor TR2 _(amp), and a selection transistor TR2_(sel) constituting the control unit for the second imaging element arefurther provided.

The reset transistor TR2 _(rst) is configured with a gate portion, achannel forming region, and source/drain regions. The gate portion ofthe reset transistor TR2 _(rst) is connected to the reset line RST₂, theone source/drain region of the reset transistor TR2 _(rst) is connectedto the power source V_(DD), and the other source/drain region thereofserves as a second floating diffusion layer FD₂.

The amplification transistor TR2 _(amp) is configured with a gateportion, a channel forming region, and source/drain regions. The gateportion is connected to the other source/drain region (second floatingdiffusion layer FD₂) of the reset transistor TR2 _(rst). In addition,the one source/drain region thereof shares the region with the othersource/drain region constituting the reset transistor TR2 _(rst) and isconnected to the power source V_(DD).

The selection transistor TR2 _(sel) is configured with a gate portion, achannel forming region, and source/drain regions. The gate portion isconnected to the select line SEL₂. In addition, the one source/drainregion thereof shares the region with the other source/drain regionconstituting the amplification transistor TR2 _(amp), and the othersource/drain region is connected to the signal line (data output line)VSL₂.

The third imaging element includes an n-type semiconductor region 43provided to the semiconductor substrate 70 as a photoelectric conversionlayer. The gate portion 46 of the transfer transistor TR3 _(trs) isconnected to the transfer gate line TG₃. In addition, a third floatingdiffusion layer FD₃ is provided to the region 46C of the semiconductorsubstrate 70 in the vicinity of the gate portion 46 of the transfertransistor TR3 _(trs). The charges stored in the n-type semiconductorregion 43 are read out to the third floating diffusion layer FD₃ througha transfer channel 46A formed along the gate portion 46.

In the third imaging element, in the first surface side of thesemiconductor substrate 70, a reset transistor TR3 _(rst), anamplification transistor TR3 _(amp), and a selection transistor TR3_(sel) constituting the control unit for the third imaging element arefurther provided.

The reset transistor TR3 _(rst) is configured with a gate portion, achannel forming region, and source/drain regions. The gate portion ofthe reset transistor TR3 _(rst) is connected to the reset line RST₃, theone source/drain region of the reset transistor TR3 _(rst) is connectedto the power source VDD, and the other source/drain region thereofserves as a third floating diffusion layer FD₃.

The amplification transistor TR3 _(amp) is configured with a gateportion, a channel forming region, and source/drain regions. The gateportion is connected to the other source/drain region (third floatingdiffusion layer FD₃) of the reset transistor TR3 _(rst). In addition,the one source/drain region thereof shares the region with the othersource/drain region constituting the reset transistor TR3 _(rst) and isconnected to the power source V_(DD).

The selection transistor TR3 _(sel) is configured with a gate portion, achannel forming region, and source/drain regions. The gate portion isconnected to the select line SEL₃. In addition, the one source/drainregion shares the region with the other source/drain region constitutingthe amplification transistor TR3 _(amp), and the other source/drainregion thereof is connected to the signal line (data output line) VSL₃.

The reset lines RST₁, RST₂, and RST₃, the select lines SEL₁, SEL₂, andSEL₃, and the transfer gate lines TG₂ and TG₃ are connected to thevertical driving circuit 112 constituting the driving circuit, and thesignal lines (data output lines) VSL₁, VSL₂, and VSL₃ are connected to acolumn signal processing circuit 113 constituting the driving circuit.

A p+ layer 44 is provided between the n-type semiconductor region 43 andthe surface 70A of the semiconductor substrate 70, so that theoccurrence of dark current is suppressed. A p+ layer 42 is formedbetween the n-type semiconductor region 41 and the n-type semiconductorregion 43, and a portion of the side surface of the n-type semiconductorregion 43 is surrounded by the p+ layer 42. A p+ layer 73 is formed inthe back surface 70B side of the semiconductor substrate 70, and An HfO₂film 74 and an insulating film 75 are formed in a portion inside thesemiconductor substrate 70 where the contact hole portion 61 is to beformed from the p+ layer 73. In the interlayer insulating layer 76,although wire lines are formed over multiple layers, the illustration isomitted.

The HfO2 film 74 is a film having negative fixed charges, and bypreparing such a film, the occurrence of dark current can be suppressed.Note that, instead of the HfO₂ film, there may be used an aluminum oxide(Al₂O₃) film, a zirconium oxide (ZrO₂) film, a tantalum oxide (Ta₂O₅)film, a titanium oxide (TiO₂) film, a lanthanum oxide (La₂O₃) film, apraseodymium oxide (Pr₂O₃) film, a cerium oxide (CeO₂) film, a neodymiumoxide (Nd₂O₃) film, a promethium oxide (Pm₂O₃) film, a samarium oxide(Sm₂O₃) film, an europium oxide (Eu₂O₃) film, a gadolinium oxide((Gd₂O₃) film, a terbium oxide (Tb₂O₃) film, a dysprosium oxide (Dy₂O₃)film, a holmium oxide (Ho₂O₃) film, a thulium oxide (Tm₂O₃) film, aytterbium oxide (Yb₂O₃) film, a lutetium oxide (Lu₂O₃) film, a yttriumoxide (Y₂O₃) film, a hafnium nitride film, an aluminum nitride film, ahafnium oxynitride film, or an aluminum oxynitride film. As a filmformation method for these films, there may be exemplified a CVD method,a PVD method, and an ALD method.

Hereinafter, operations of the imaging element (first imaging element)of Example 1 will be described with reference to FIG. 5. Herein, thepotential of the first electrode 11 is set to be higher than thepotential of the second electrode. Namely, for example, when the firstelectrode 11 is set to a positive potential and the second electrode isset to a negative potential, electrons are read out to the floatingdiffusion layer through photoelectric conversion in the photoelectricconversion layer 15. A similar operation is performed in other examples.Note that, in a form where, when the first electrode 11 is set to anegative potential and the second electrode is set to a positivepotential, holes are read out to the floating diffusion layer throughthe photoelectric conversion in the photoelectric conversion layer 15,the levels of the potentials hereinafter mentioned may be set to beopposite.

Reference numerals used in FIG. 5, FIG. 20, and FIG. 21 in Example 4 aredescribed later, and FIGS. 32 and 33 in Example 6 described later are asfollows.

PA . . . the potential of a point PA of the region of the photoelectricconversion layer 15 facing the charge storage electrode 12 or thepotential of a point PA of the region of the photoelectric conversionlayer 15 facing the charge storage electrode segment 12C;

PB . . . the potential of a point PB of the region of the photoelectricconversion layer 15 facing a region located in the middle between thecharge storage electrode 12 and the first electrode 11, the potential ofa point PB of the region of the photoelectric conversion layer 15 facingtransfer control electrode (charge transfer electrode) 13, or thepotential of a point PB of the region of the photoelectric conversionlayer 15 facing the charge storage electrode segment 12B;

PC . . . the potential of a point PC of the region of the photoelectricconversion layer 15 facing the first electrode 11 or the potential of apoint PC of the region of the photoelectric conversion layer 15 facingthe charge storage electrode segment 12A;

PD . . . the potential of a point PD of the region of the photoelectricconversion layer 15 facing a region located in the middle between thecharge storage electrode segment 12C and the first electrode 11;

FD . . . the potential of the first floating diffusion layer FD₁;

VOA . . . the potential of the charge storage electrode 12.

VOA-A . . . the potential of the charge storage electrode segment 12A;

VOA-B . . . the potential of the charge storage electrode segment 12B;

VOA-C . . . the potential of the charge storage electrode segment 12C;

VOT . . . the potential of the transfer control electrode (chargetransfer electrode) 13;

RST . . . the potential of the gate portion 51 of the reset transistorTR1 _(rst);

VDD . . . the potential of the power source;

VSL_1 . . . the signal line (data output line) VSL₁;

TR1_rst . . . the reset transistor TR1 _(rst);

TR1_amp . . . the amplification transistor TR1 _(amp); and

TR1_sel . . . the selection transistor TR1 _(sel).

In a charge storage period, a potential V₁₁ is applied from the drivingcircuit to the first electrode 11, and a potential V₁₂ is applied fromthe driving circuit to the charge storage electrode 12. By the lightincident on the photoelectric conversion layer 15, photoelectricconversion occurs in the photoelectric conversion layer 15. The holesgenerated through the photoelectric conversion are transferred from thesecond electrode 16 through the wire line V_(OU) to the driving circuit.On the other hand, since the potential of the potential of the firstelectrode 11 is set to be higher than the potential of the secondelectrode 16, namely, for example, since a positive potential is appliedto the first electrode 11 and a negative potential is applied to thesecond electrode 16, it is set that V₁₂≥V₁₁, preferably, V₁₂>V₁₁.Therefore, the electrons generated through the photoelectric conversionare attracted by the charge storage electrode 12, and thus, theelectrons are stopped in the region of the photoelectric conversionlayer 15 facing the charge storage electrode 12. Namely, the charges arestored in the photoelectric conversion layer 15. Since V₁₂>V₁₁, theelectrons generated in the inner portion of the photoelectric conversionlayer 15 do not move toward the first electrode 11. As the time of thephotoelectric conversion elapses, the potential of the region of thephotoelectric conversion layer 15 facing the charge storage electrode 12becomes a further negative value.

In the last stage of the charge storage period, a reset operation isperformed. Therefore, the potential of the first floating diffusionlayer FD₁ is reset, and the potential of the first floating diffusionlayer FD₁ becomes the potential V_(DD) of the power source.

After the completion of the reset operation, charge read-out isperformed. Namely, in the charge transfer period, from the drivingcircuit, a potential V₂₁ is applied to the first electrode 11, and apotential V₂₂ is applied to the charge storage electrode 12. Herein, itis set that V₂₂<V₂₁. By doing so, the electrons, which have stopped inthe region of the photoelectric conversion layer 15 facing the chargestorage electrode 12, are read out to the first electrode 11,furthermore, to the first floating diffusion layer FD₁. Namely, thecharges stored in the photoelectric conversion layer 15 are read out tothe control unit.

The structure which includes the insulation layer 82 between the chargestorage electrode 12 and the first electrode 11 can curb variation ofthe PB electric potential. Without the insulation layer 82 at such aposition, the various positions of the edge of the insulation layer 82can cause a variation of the PB electric potential in addition to adistance between the charge storage electrode 12 and the first electrode11. On the contrary, the presence of the insulation layer 82 in anopening between the charge storage electrode 12 and the first electrode11 allows the distance between the charge storage electrode 12 and thefirst electrode 11 to determine the effect of the PB electric potentialbecause. Thus, by including insulation layer 82 as mentioned above, theinsulation layer 82 may cause the minimum PB electric potential toincrease which effectively confines electrons to the PA position andfurther reduces a leakage of electric current.

In this manner described heretofore, a series of the operations of thecharge storage, the reset operation, and the charge transfer iscompleted.

The operations of the amplification transistor TR1 _(amp) and theselection transistor TR1 _(sel) after the read-out of the electrons tothe first floating diffusion layer FD₁ are the same as the operations ofsuch transistors in the related art. In addition, a series of operationsof the charge storage, the reset operation, and the charge transfer ofthe second imaging element and third imaging element is similar to aseries of operations of the charge storage, the reset operation, and thecharge transfer in the related art. In addition, similarly to therelated art, reset noise of the first floating diffusion layer FD₁ canbe removed by a correlated double sampling (CDS) process.

As described above, in Example 1, since the charge storage electrode,which is arranged to be separated from the first electrode and isarranged to face the photoelectric conversion layer with the insulatinglayer interposed therebetween, is provided, when the photoelectricconversion unit is illuminated with light and the photoelectricconversion is performed in the photoelectric conversion unit, a kind ofcapacitor is formed by the, photoelectric conversion layer, theinsulating layer, and the charge storage electrode, so that the chargescan be stored in the photoelectric conversion layer. Therefore, at thetime of starting exposure, by completely depleting a charge storageunit, it is possible to erase the charges. As a result, it is possibleto suppress the occurrence of the phenomenon of an increase in kTCnoise, deterioration in random noise, and a deterioration in imagequality in the imaging. In addition, since the entire pixels can bereset at one time, a so-called global shutter function can beimplemented.

A conceptual diagram of a solid-state imaging device of Example 1 isillustrated in FIG. 8. The solid-state imaging device 100 of Example 1is configured to include an imaging region 111 where stacked-typeimaging elements 101 are arranged in a two-dimensional array shape anddriving circuits (peripheral circuits) such as a vertical drivingcircuit 112, a column signal processing circuit 113, a horizontaldriving circuit 114, an output circuit 115, and a driving controlcircuit 116. Note that, these circuits may be configured with well-knowncircuits. It is obvious that these circuits may also be configured byusing other circuit configurations (for example, various circuits usedfor a CCD imaging device or a CMOS imaging device in the related art.Note that, in FIG. 8, the stacked-type imaging elements 101 of only onerow are indicated by reference numerals “101.”

The driving control circuit 116 generates a clock signal and a controlsignal which become references of operations of the vertical drivingcircuit 112, the column signal processing circuit 113, and thehorizontal driving circuit 114 on the basis of a verticalsynchronization signal, a horizontal synchronization signal and a masterclock. Then, the generated clock signal or control signal is input tothe vertical driving circuit 112, the column signal processing circuit113, and the horizontal driving circuit 114.

The vertical driving circuit 112 is configured with, for example, shiftregisters and selectively scans the stacked-type imaging elements 101 ofthe imaging region 111 sequentially in unit of a row in the verticaldirection. Then, a pixel signal (image signal) based on a current(signal) generated according to a received light amount of eachstacked-type imaging element 101 is transmitted through the signal line(data output line) 117 and VSL to the column signal processing circuit113.

The column signal processing circuit 113 is arranged, for example, forevery column of the stacked-type imaging elements 101 and performs asignal process such as noise removal or signal amplification on theimage signal output from one row of the stacked-type imaging elements101 according to a signal from a black reference pixel (not shown butformed in the periphery of an effective pixel region) for every imagingelement.

A horizontal selection switch (not shown) is provided to be connectedbetween the output stage of the column signal processing circuit 113 andthe horizontal signal line 118.

The horizontal driving circuit 114 is configured with, for example,shift registers and sequentially selects the column signal processingcircuits 113 by sequentially outputting horizontal scan pulses to outputsignals of the column signal processing circuits 113 to the horizontalsignal line 118.

The output circuit 115 performs a signal process on the signalssequentially supplied from the column signal processing circuits 113through the horizontal signal line 118 and outputs the signals.

An equivalent circuit diagram of a modified example of the imagingelement and the stacked-type imaging element of Example 1 is illustratedin FIG. 9. As a schematic layout view of a first electrode and a chargestorage electrode constituting a modified example of the imaging elementof Example 1 and transistors constituting a control unit is illustratedin FIG. 10, the other source/drain region 51B of the reset transistorTR1 _(rst) may be grounded instead of being connected to the powersource V_(DD).

The imaging element and the stacked-type imaging element of Example 1may be manufactured, for example, by the method described hereinafter.Namely, first, an SOI substrate is prepared. Then, a first silicon layeris formed on the surface of the SOI substrate on the basis of anepitaxial growth method, and a p+ layer 73 and an n-type semiconductorregion 41 are formed on the first silicon layer. Next, a second siliconlayer is formed on the first silicon layer on the basis of an epitaxialgrowth method, and an element isolation region 71, an oxide film 72, ap+ layer 42, an n-type semiconductor region 43, and a p+ layer 44 areformed on the second silicon layer. In addition, various transistors andthe like constituting a control unit of the imaging element are formedin the second silicon layer, and a wire line layer 62, an interlayerinsulating layer 76, and various wire lines are formed thereon. Theinterlayer insulating layer 76 and a support substrate (not shown) areallowed to be adhered to each other. After that, by removing the SOIsubstrate, the first silicon layer is exposed. Note that the surface ofthe second silicon layer corresponds to the surface 70A of thesemiconductor substrate 70, and the surface of the first silicon layercorresponds to the back surface 70B of the semiconductor substrate 70.In addition, the first silicon layer and the second silicon layer arecollectively expressed as the semiconductor substrate 70. Next, in theback surface 70B side of the semiconductor substrate 70, an openingportion for forming a contact hole portion 61 is formed; an HfO₂ film74, an insulating film 75, and the contact hole portion 61 are formed;and pad portions 63 and 64, an interlayer insulating layer 81,connection holes 65 and 66, a first electrode 11, a charge storageelectrode 12, and an insulating layer 82 are formed. Next, a connectionportion 67 is opened, and a photoelectric conversion layer 15, a secondelectrode 16, a protective layer 83, and an on-chip microlens 90 areformed. By doing so, the imaging element and the stacked-type imagingelement of Example 1 can be obtained.

EXAMPLE 2

Example 2 is a modification of Example 1. An imaging element and astacked-type imaging element of Example 2 of which a schematic partialcross-sectional view is illustrated in FIG. 11 are a front-illuminatedtype imaging element and a front-illuminated type stacked-type imagingelement and have a stacked structure of three imaging elements of afirst-type green imaging element (first imaging element) of Example 1being sensitive to green and having a first-type green photoelectricconversion layer absorbing green light, a second-type blue imagingelement (second imaging element) of the related art being sensitive toblue and having a second-type blue photoelectric conversion layerabsorbing blue light, and a second-type red imaging element (thirdimaging element) of the related art being sensitive to red and having asecond-type red photoelectric conversion layer absorbing red light.Herein, the red imaging element (third imaging element) and the blueimaging element (second imaging element) are provided in thesemiconductor substrate 70, and the second imaging element is located tobe closer to the light-incident side than the third imaging element. Inaddition, the green imaging element (first imaging element) is providedabove the blue imaging element (second imaging element).

Similarly to Example 1, various transistors constituting the controlunit are provided in the surface 70A side of the semiconductor substrate70. These transistors may be formed with substantially a similarconfiguration and structure to those of the transistors described inExample 1. In addition, although the second imaging element and thethird imaging element are provided in the semiconductor substrate 70,these imaging elements may be formed with substantially a similarconfiguration and structure to those of the second imaging element andthe third imaging element described in Example 1.

Interlayer insulating layers 77 and 78 are formed on the surface 70A ofthe semiconductor substrate 70, and the photoelectric conversion unit(the first electrode 11, the photoelectric conversion layer 15, and thesecond electrode 16), the charge storage electrode 12, and the likeconstituting the imaging element of Example 1 are provided on theinterlayer insulating layer 78.

In this manner, except that the imaging element and the stacked-typeimaging element are of the front-illuminated type, since theconfiguration and structure of the imaging element and the stacked-typeimaging element of Example 2 can be formed to be similar to theconfiguration and structure of the imaging element and the stacked-typeimaging element of Example 1, the detailed description is omitted.

EXAMPLE 3

Example 3 is a modification of Examples 1 and 2.

An imaging element and a stacked-type imaging element of Example 3 ofwhich a schematic partial cross-sectional view is illustrated in FIG. 12are a back-illuminated type imaging element and a back-illuminated typestacked-type imaging element and have a stacked structure of two imagingelements of a first-type first imaging element of Example 1 and asecond-type second imaging element. In addition, modified examples ofthe imaging element and the stacked-type imaging element of Example 3 ofwhich a schematic partial cross-sectional view is illustrated in FIG. 13are a front-illuminated type imaging element and a front-illuminatedtype stacked-type imaging element and have a stacked structure of twoimaging elements of a first-type first imaging element of Example 1 anda second-type second imaging element. Herein, the first imaging elementabsorbs primary color light, and the second imaging element absorbscomplementary color light. Alternatively, the first imaging elementabsorbs white light, and the second imaging element absorbs an infraredray.

A modified example of the imaging element of Example 3 of which aschematic partial cross-sectional view is illustrated in FIG. 14 is aback-illuminated type imaging element and is configured with afirst-type first imaging element of Example 1. Alternatively, a modifiedexample of the imaging element of Example 3 of which a schematic partialcross-sectional view is illustrated in FIG. 15A is a front-illuminatedtype imaging element and is configured with a first-type first imagingelement of Example 1. Herein, the first imaging element is configuredwith three types of imaging elements of an imaging element absorbing redlight and an imaging element absorbing green light, and an imagingelement absorbing blue light. Furthermore, the solid-state imagingdevice according to the first embodiment of the present disclosure isconfigured with a plurality of the imaging elements. As an array of aplurality of the imaging elements, there may be exemplified a Bayerarray. If necessary, color filters for performing spectral separation ofblue light, green light, and red light are arranged in thelight-incident side of each imaging element. Moreover, and as depictedin FIGS. 15B-D, the insulating layer 82 may include multiple layers. Asdepicted in FIGS. 15B-D, the insulating layer 82 may include multiplelayers 82E and 82F. For example, a first region of the insulatingmaterial 82 between the charge storage electrode 12 and thephotoelectric conversion layer 15 may exist, and a second region of theinsulating material 82 between the charge storage electrode 12 and thefirst electrode 11 may exist. In some embodiments, the second region ofthe insulating material includes a first insulating layer 82E includingthe insulating material and a second insulating layer 82F including theinsulating material, and the first insulating material 82F is stacked onthe second insulating material 82E. FIGS. 15B-D further depict variousconfigurations with respect to the insulating layer 82 (e.g., theconfigurations of layers 82E and 82F change).

Note that, instead of preparing one first-type imaging element ofExample 1, two imaging elements may be stacked (namely, the twophotoelectric conversion units are stacked and the control units for thetwo imaging elements are prepared in the semiconductor substrate), orthree imaging elements may be stacked (namely, the three photoelectricconversion units are stacked and the control units for the three imagingelements are prepared in the semiconductor substrate). Examples of thestacked structures of the first-type imaging element and the second-typeimaging element are listed in the following table.

TABLE 1 Reference First type Second type FIG. Back- 1 Green 2 Blue + RedFIG. 1.A-D illuminated FIG. 11 type and 1 Primary color 1 ComplementaryFIG. 12 front- color FIG. 13 illuminated 1 White 1 Infrared ray type 1Blue or Green or 0 FIG. 14 Red FIG. 15A-D 2 Green + Infrared 2 Blue +Red light 2 Green + Blue 1 Red 2 White + Infrared 0 light 3 Green +Blue + 2 Bluish green Red (Emerald Color) + Infrared light 3 Green +Blue + 1 Infrared light Red 3 Blue + Green + 0 Red

EXAMPLE 4

Example 4 is a modification of Examples 1 to 3 and relates to an imagingelement or the like according to an embodiment of the present disclosurehaving transfer control electrode (charge transfer electrode). Aschematic partial cross-sectional view of a portion of the imagingelement and the stacked-type imaging element of Example 4 is illustratedin FIG. 16. Equivalent circuit diagrams of the imaging element and thestacked-type imaging element of Example 4 are illustrated in FIGS. 17and 18. A schematic layout view of a first electrode, a transfer controlelectrode, and a charge storage electrode constituting the imagingelement of Example 4 and transistors constituting a control unit isillustrated in FIG. 19. Potential states of components in an operationperiod of the imaging element of Example 4 are illustrated in FIGS. 20and 21. In addition, a schematic layout view of the first electrode, thetransfer control electrode, and the charge storage electrodeconstituting the imaging element of Example 4 is illustrated in FIG. 22.A schematic perspective view of the first electrode, the transfercontrol electrode, the charge storage electrode, a second electrode, anda contact hole portion constituting the imaging element of Example 4 isillustrated in FIG. 23.

The imaging element and the stacked-type imaging element of Example 4are configured to further include a transfer control electrode (chargetransfer electrode) 13 which is arranged between the first electrode 11and the charge storage electrode 12 to be separated from the firstelectrode 11 and the charge storage electrode 12 and is arranged to facethe photoelectric conversion layer 15 through the insulating layer 82.The transfer control electrode 13 is connected to the pixel drivingcircuit constituting the driving circuit through a connection hole 68B,a pad portion 68A, and a wire line V_(OT) provided in the interlayerinsulating layer 81. Note that, various components of the imagingelement located below the interlayer insulating layer 81 arecollectively denoted by reference numeral 91 for the convenience inorder to simplify the drawings.

Hereinafter, operations of the imaging element (first imaging element)of Example 4 will be described with reference to FIGS. 20 and 21. Notethat FIG. 20 and FIG. 21 are different from each other, particularly, interms of the potential applied to the charge storage electrode 12 andthe potential of the point PB.

In the charge storage period, from the driving circuit, a potential V₁₁is applied to the first electrode 11, a potential V₁₂ is applied to thecharge storage electrode 12, and a potential V₁₃ is applied to thetransfer control electrode 13. By the light incident on thephotoelectric conversion layer 15, photoelectric conversion occurs inthe photoelectric conversion layer 15. The holes generated through thephotoelectric conversion are transferred from the second electrode 16through the wire line V_(OU) to the driving circuit. On the other hand,since the potential of the potential of the first electrode 11 is set tobe higher than the potential of the second electrode 16, namely, forexample, since a positive potential is applied to the first electrode 11and a negative potential is applied to the second electrode 16, it isset that V₁₂>V₁₃ (for example, V₁₂>V₁₁>V₁₃, or V₁₁>V₁₂>V₁₃). Therefore,the electrons generated through the photoelectric conversion areattracted by the charge storage electrode 12, and thus, the electronsare stopped in the region of the photoelectric conversion layer 15facing the charge storage electrode 12. Namely, the charges are storedin the photoelectric conversion layer 15. Since V₁₂>V₁₃, it is possibleto reliably prevent the electrons generated in the photoelectricconversion layer 15 from moving toward the first electrode 11. As thetime of the photoelectric conversion elapses, the potential of theregion of the photoelectric conversion layer 15 facing the chargestorage electrode 12 becomes a further negative value.

In the last stage of the charge storage period, a reset operation isperformed. Therefore, the potential of the first floating diffusionlayer FD₁ is reset, and the potential of the first floating diffusionlayer FD₁ becomes the potential V_(DD) of the power source.

After the completion of the reset operation, charge read-out isperformed. Namely, in the charge transfer period, from the drivingcircuit, a potential V₂₁ is applied to the first electrode 11, apotential V₂₂ is applied to the charge storage electrode 12, and apotential V₂₃ is applied to the transfer control electrode 13. Herein,it is set that V₂₂≤V₂₃≤V₂₁. By doing so, the electrons, which havestopped in the region of the photoelectric conversion layer 15 facingthe charge storage electrode 12, are reliably read out to the firstelectrode 11, and furthermore, to the first floating diffusion layerFD₁. Namely, the charges stored in the photoelectric conversion layer 15are read out to the control unit.

In this manner described heretofore, a series of the operations of thecharge storage, the reset operation, and the charge transfer iscompleted.

The operations of the amplification transistor TR1 _(amp) and theselection transistor TR1 _(sel) after the read-out of the electrons tothe first floating diffusion layer FD₁ are the same as the operations ofsuch transistors in the related art. In addition, a series of operationsof the charge storage, the reset operation, and the charge transfer of,for example, the second imaging element and third imaging element issimilar to a series of operations of the charge storage, the resetoperation, and the charge transfer in the related art.

As a schematic layout view of the first electrode and the charge storageelectrode constituting a modified example of the imaging element ofExample 4 and transistors constituting a control unit is illustrated inFIG. 24, the other source/drain region 51B of the reset transistor TR1_(rst) may be grounded instead of being connected to the power sourceV_(DD).

EXAMPLE 5

Example 5 is a modification of Examples 1 to 4 relates to an imagingelement or the like according to an embodiment of the present disclosurehaving a charge ejection electrode. A schematic partial cross-sectionalview of a portion of the imaging element and the stacked-type imagingelement of Example 5 is illustrated in FIG. 25. A schematic layout viewof a first electrode, a charge storage electrode, and a charge ejectionelectrode constituting the imaging element of Example 5 is illustratedin FIG. 26. A schematic perspective view of the first electrode, thecharge storage electrode, the charge ejection electrode, a secondelectrode, and a contact hole portion constituting the imaging elementof Example 5 is illustrated in FIG. 27.

In the imaging element and the stacked-type imaging element of Example5, the imaging element is configured to further include a chargeejection electrode 14, which is connected through a connection portion69 to a photoelectric conversion layer 15 and is arranged to beseparated from the first electrode 11 and the charge storage electrode12. The charge ejection electrode 14 is arranged to surround the firstelectrode 11 and the charge storage electrode 12 (namely, in a frameshape). The charge ejection electrode 14 is connected to the pixeldriving circuit constituting the driving circuit. The photoelectricconversion layer 15 extends in the connection portion 69. Namely, thephotoelectric conversion layer 15 extends in the second opening portion85 provided in the insulating layer 82 to be connected to the chargeejection electrode 14. The charge ejection electrode 14 is shared(commonly used) by a plurality of the imaging elements.

In Example 5, in the charge storage period, from the driving circuit, apotential V₁₁ is applied to the first electrode 11, a potential V₁₂ isapplied to the charge storage electrode 12, and a potential V₁₄ isapplied to the charge ejection electrode 14, so that the charges arestored in the photoelectric conversion layer 15. By the light incidenton the photoelectric conversion layer 15, photoelectric conversionoccurs in the photoelectric conversion layer 15. The holes generatedthrough the photoelectric conversion are transferred from the secondelectrode 16 through the wire line V_(OU) to the driving circuit. On theother hand, since the potential of the potential of the first electrode11 is set to be higher than the potential of the second electrode 16,namely, for example, since a positive potential is applied to the firstelectrode 11 and a negative potential is applied to the second electrode16, it is set that V₁₄>V₁₁ (for example, V₁₂>V₁₄>V₁₁). Therefore, theelectrons generated through the photoelectric conversion are attractedby the charge storage electrode 12, and thus, the electrons are stoppedin the region of the photoelectric conversion layer 15 facing the chargestorage electrode 12, so that it is possible to reliably prevent theelectrons from moving toward the first electrode 11. However, theelectrons (so-called overflowed electrons), which are not sufficientlyattracted by the charge storage electrode 12 or not stored in thephotoelectric conversion layer 15, are transferred through the chargeejection electrode 14 to the driving circuit.

In the last stage of the charge storage period, a reset operation isperformed. Therefore, the potential of the first floating diffusionlayer FD₁ is reset, and the potential of the first floating diffusionlayer FD₁ becomes the potential V_(DD) of the power source.

After the completion of the reset operation, charge read-out isperformed. Namely, in the charge transfer period, from the drivingcircuit, a potential V₂₁ is applied to the first electrode 11, apotential V₂₂ is applied to the charge storage electrode 12, and apotential V₂₄ is applied to the charge ejection electrode 14. Herein, itis set that V₂₄<V₂₁ (for example, V₂₄<V₂₂<V₂₁). By doing so, theelectrons, which have stopped in the region of the photoelectricconversion layer 15 facing the charge storage electrode 12, are reliablyread out to the first electrode 11, and furthermore, to the firstfloating diffusion layer FD₁. Namely, the charges stored in thephotoelectric conversion layer 15 are read out to the control unit.

In this manner described heretofore, a series of the operations of thecharge storage, the reset operation, and the charge transfer iscompleted.

The operations of the amplification transistor TR1 _(amp) and theselection transistor TR1 _(sel) after the read-out of the electrons tothe first floating diffusion layer FD₁ are the same as the operations ofsuch transistors in the related art. In addition, a series of operationsof the charge storage, the reset operation, and the charge transfer of,for example, the second imaging element and third imaging element issimilar to a series of operations of the charge storage, the resetoperation, and the charge transfer in the related art.

In Example 5, since the overflowed electrons are transferred to thedriving circuit through the charge ejection electrode 14, leakage out tothe charge storage units of the adjacent pixels can be suppressed, sothat it is possible to suppress the occurrence of blooming. Furthermore,therefore, it is possible to improve imaging performance of the imagingelement.

EXAMPLE 6

Example 6 is a modification of Examples 1 to 5 and relates to an imagingelement or the like according to an embodiment of the present disclosurehaving a plurality of charge storage electrode segments.

A schematic partial cross-sectional view of a portion of the imagingelement of Example 6 is illustrated in FIG. 28. Equivalent circuitdiagrams of the imaging element and the stacked-type imaging element ofExample 6 are illustrated in FIGS. 29 and 30. A schematic layout view ofa first electrode and a charge storage electrode constituting theimaging element of Example 6 and transistors constituting a control unitis illustrated in FIG. 31. Potential states of components in anoperation period of the imaging element of Example 6 are illustrated inFIGS. 32 and 33. In addition, a schematic layout view of the firstelectrode and the charge storage electrode constituting the imagingelement of Example 6 is illustrated in FIG. 34. A schematic perspectiveview of the first electrode, the charge storage electrode, a secondelectrode, and a contact hole portion constituting the imaging elementof Example 6 is illustrated in FIG. 35.

In Example 6, the charge storage electrode 12 is configured with aplurality of charge storage electrode segments 12A, 12B, and 12C. Thenumber of charge storage electrode segments may be two or more, and inExample 6, the number is set to “3”. Then, in the imaging element andthe stacked-type imaging element of Example 6, since the potential ofthe first electrode 11 is higher than the potential of the secondelectrode 16, namely, for example, since a positive potential is appliedto the first electrode 11 and a negative potential is applied to thesecond electrode 16, in the charge transfer period, the potentialapplied to the charge storage electrode segment 12A located at theposition closest to the first electrode 11 is higher than the potentialapplied to the charge storage electrode segment 12C located at theposition farthest from the first electrode 11. In this manner, potentialgradient is provided to the charge storage electrode 12, so that theelectrons, which have stopped in the region of the photoelectricconversion layer 15 facing the charge storage electrode 12, are morereliably read out to the first electrode 11, and furthermore, to thefirst floating diffusion layer FD₁. Namely, the charges stored in thephotoelectric conversion layer 15 are read out to the control unit.

In the example illustrated in FIG. 32, in the charge transfer period, itis set that the potential of the charge storage electrode segment12C<the potential of the charge storage electrode segment 12B<thepotential of the charge storage electrode segment 12A, and thus, theelectrons, which have stopped in the region of the photoelectricconversion layer 15, are read out to the first floating diffusion layerFD₁ at one time. On the other hand, in the example illustrated in FIG.33, in the charge transfer period, the potential of the charge storageelectrode segment 12C, the potential of the charge storage electrodesegment 12B, and the potential of the charge storage electrode segment12A are allowed to be gradually changed (namely, changed stepwise or ina slope shape). Therefore, the electrons, which have stopped in theregion of the photoelectric conversion layer 15 facing the chargestorage electrode segment 12C, are allowed to be moved to thephotoelectric conversion layer 15 facing the charge storage electrodesegment 12B. Subsequently, the electrons, which have stopped in theregion of the photoelectric conversion layer 15 facing the chargestorage electrode segment 12B, are allowed to be moved to thephotoelectric conversion layer 15 facing the charge storage electrodesegment 12A. Subsequently, the electrons, which have stopped in theregion of the photoelectric conversion layer 15 facing the chargestorage electrode segment 12A, are allowed to be reliably read out tothe first floating diffusion layer FD₁.

As a schematic layout view of a first electrode and a charge storageelectrode constituting a modified example of the imaging element ofExample 6 and transistors constituting a control unit is illustrated inFIG. 36, the other source/drain region 51B of the reset transistor TR1_(rst) may be grounded instead of being connected to the power sourceV_(DD).

Heretofore, although the present disclosure is described on the basis ofthe preferred examples, the present disclosure is not limited to theexamples. The structure, configuration, manufacturing conditions,manufacturing methods, and used materials of the imaging elements,stacked-type imaging elements, and solid-state imaging devices describedin the example are exemplary ones, and thus, these are appropriatelychanged. Besides the form where one floating diffusion layer is providedto one imaging element, there may be implemented a form where onefloating diffusion layer is provided to a plurality of imaging elements.Namely, by appropriately controlling a timing of the charge transferperiod, a plurality of the imaging elements can be allowed to share onefloating diffusion layer. Furthermore, in this case, a plurality of theimaging elements can also be allowed to share one contact hole portion.

As a modified example of the imaging element and the stacked-typeimaging element described in Example 1 is illustrated in FIG. 37, thefirst electrode 11 may be configured to extend in an opening portion 84Aprovided to the insulating layer 82 to be connected to the photoelectricconversion layer 15.

Alternatively, as a modified example of the imaging element and thestacked-type imaging element described in Example 1 is illustrated inFIG. 38 and a schematic enlarged partial cross-sectional view of aportion and the like of the first electrode is illustrated in FIG. 39A,the edge of the top surface of the first electrode 11 is covered withthe insulating layer 82; the first electrode 11 is exposed to the bottomsurface of an opening portion 84B; and when the surface of theinsulating layer 82 being in contact with the top surface of the firstelectrode 11 is defined by a first surface 82 a and the surface of theinsulating layer 82 being in contact with the portion of thephotoelectric conversion layer 15 facing the charge storage electrode 12is defined by a second surface 82 b, the side surface of the openingportion 84B has a slope expanding from the first surface 82 a toward thesecond surface 82 b. In this manner, since a slope is provided to theside surface of the opening portion 84B, the charge more smoothly movesfrom the photoelectric conversion layer 15 to the first electrode 11.Note that, in the example illustrated in FIG. 39A, the axial line of theopening portion 84B is used as a center, and the side surface of theopening portion 84B has a rotation symmetry. However, as illustrated inFIG. 39B, the opening portion 84C may be provided so that the sidesurface of the opening portion 84C having a slope expanding from thefirst surface 82 a toward the second surface 82 b is located in thecharge storage electrode 12 side. Therefore, the charges from theportion of the photoelectric conversion layer 15 at the side opposite tothe charge storage electrode 12 with the opening portion 84C interposedtherebetween are hard to move. In addition, although the side surface ofthe opening portion 84B has a slope expanding from the first surface 82a toward the second surface 82 b, the edge of the side surface of theopening portion 84B in the second surface 82 b may be located in theouter side from the edge of the first electrode 11 as illustrated inFIG. 39A or may be located in the side inner from the edge of the firstelectrode 11 as illustrated in FIG. 39C. By employing the formerconfiguration, the charge transfer can be more easily performed; and byemploying the latter configuration, the shape irregularity at the timeof forming the opening portion can be reduced.

The opening portions 84B and 84C can be formed by reflowing an etchingmask made of a resist material formed at the time of forming the openingportion in the insulating layer on the basis of an etching method toprovide a slope to the side surface of an opening portion of an etchingmask and by etching the insulating layer 82 by using the etching mask.

Alternatively, with respect to the charge ejection electrode 14described in Example 5, as illustrated in FIG. 40, the photoelectricconversion layer 15 may be formed to extend in a second opening portion85A provided to the insulating layer 82 to be connected to the chargeejection electrode 14; the edge of the top surface of the chargeejection electrode 14 is covered with the insulating layer 82; thecharge ejection electrode 14 is exposed in the bottom surface of thesecond opening portion 85A; and when the surface of the insulating layer82 being in contact with the top surface of the charge ejectionelectrode 14 is defined by a third surface 82c and the surface of theinsulating layer 82 being in contact with the portion of thephotoelectric conversion layer 15 facing the charge storage electrode 12is defined by a second surface 82 b, the side surface of the secondopening portion 85A has a slope expanding from the third surface 82ctoward the second surface 82 b.

Alternatively, as a modified example of the imaging element and thestacked-type imaging element described in Example 1 is illustrated inFIG. 41, light may be configured to be incident on the side of thesecond electrode 16, and a light-shielding layer 92 may be configured tobe formed in the light-incident side of the second electrode 16. Notethat various wire lines provided to be closer to the light-incident sidethan to the photoelectric conversion layer may be allowed to function aslight-shielding layers.

Note that in the example illustrated in FIG. 41, although thelight-shielding layer 92 is formed above the second electrode 16,namely, although the light-shielding layer 92 is formed above the firstelectrode 11 as the light incidence side of the second electrode 16, asillustrated in FIG. 42, the light-shielding layer may be arranged on thesurface of the light incidence side of the second electrode 16. Inaddition, in some cases, as illustrated in FIG. 43, the light-shieldinglayer 92 may be formed in the second electrode 16.

Alternatively, there may be provided a structure where light is incidentfrom the second electrode 16 side, and no light is incident on the firstelectrode 11. Specifically, as illustrated in FIG. 41, thelight-shielding layer 92 is formed above the first electrode 11 as thelight-incident side of the second electrode 16. Alternatively, asillustrated in FIG. 45, there may be provided a structure where anon-chip microlens 90 is provided above the charge storage electrode 12and the second electrode 16, and light incident on the on-chip microlens90 is collected in the charge storage electrode 12, so that light maynot reach the first electrode 11. Note that as described in Example 4,in the case where the transfer control electrode 13 is provided, it ispossible to implement a form where light is not incident on the firstelectrode 11 and the transfer control electrode 13. Specifically, asillustrated in FIG. 44, there may be provided a form where thelight-shielding layer 92 is formed above the first electrode 11 and thetransfer control electrode 13. Alternatively, there may be provided astructure where the light incident on the on-chip microlens 90 does notreach the first electrode 11 and the transfer control electrode 13.

By employing the above-described configurations and structures,alternatively, providing the light-shielding layer 92 so that light isincident on only the portion of the photoelectric conversion layer 15located above the charge storage electrode 12, or alternativelydesigning the on-chip microlens 90, since the portion of thephotoelectric conversion layer 15 located above the first electrode 11(or above the first electrode 11 and the transfer control electrode 13)does not contribute to the photoelectric conversion, it is possible tomore reliably reset the entire pixels at one time, so that it ispossible to more easily implement a global shutter function. Namely, ina driving method for a solid-state imaging device including a pluralityof imaging elements having the above-described configuration andstructure, repeated are the following processes:

in all the imaging elements, at one time, charges are stored in thephotoelectric conversion layer 15, and the charges of the firstelectrode 11 are ejected to the outside; and

in all imaging elements, at one time, the charges stored in thephotoelectric conversion layer 15 are transferred to the first electrode11, and after the completion of transfer, the charges transferred to thefirst electrode 11 in the respective imaging elements are sequentiallyread out.

The photoelectric conversion layer is not limited to the configurationwhere the photoelectric conversion layer is one layer. For example, as amodified example of the imaging element and the stacked-type imagingelement described in Example 1 is illustrated in FIG. 46A, thephotoelectric conversion layer 15 may be configured to have a stackedlayer structure of, for example, a lower semiconductor layer 15A made ofIGZO and an upper photoelectric conversion layer 15B made of a materialconstituting the photoelectric conversion layer 15 described inExample 1. In this manner, by providing the lower semiconductor layer15A, it is possible to prevent recoupling in the charge storage period,so that it is possible to increase transfer efficiency of the chargesstored in the photoelectric conversion layer 15 to the first electrode11, and it is possible to suppress the occurrence of dark current. Inaddition, as a modified example of Example 4, as illustrated in FIG. 47,a plurality of the transfer control electrodes may be provided from theposition closest to the first electrode 11 toward the charge storageelectrode 12. Note that an example where two transfer control electrodes13A and 13B are provided is illustrated in FIG. 47.

As depicted in FIGS. 46B-D, the insulating layer 82 may include multiplelayers 82E and 82F. For example, a first region of the insulatingmaterial 82 between the charge storage electrode 12 and thephotoelectric conversion layer 15 may exist, and a second region of theinsulating material 82 between the charge storage electrode 12 and thefirst electrode 11 may exist. In some embodiments, the second region ofthe insulating material includes a first insulating layer 82E includingthe insulating material and a second insulating layer 82F including theinsulating material, and the first insulating material 82F is stacked onthe second insulating material 82E. FIGS. 46B-D further depict variousconfigurations with respect to the insulating layer 82 (e.g., theconfigurations of layers 82E and 82F change).

Various modified examples described hereinbefore may be appropriatelyapplied to Example 1 or other examples.

In examples, although the electrons are set as the signal charges andthe conductive type of the photoelectric conversion layer formed in thesemiconductor substrate is set as the n type, the present disclosure canbe applied to a solid-state imaging device where holes are set as thesignal charges. In this case, each semiconductor region may beconfigured as a semiconductor region having the opposite conductivetype, and the conductive type of the photoelectric conversion layerformed in the semiconductor substrate may be of p type.

In addition, in the examples, although the case of the application tothe CMOS-type solid-state imaging device where the unit pixels ofdetecting signal charges according to incident light amount as aphysical quantity are arranged in a matrix shape is exemplified in thedescription, the present disclosure is not limited to the application tothe CMOS-type solid-state imaging device, but it may be applied to aCCD-type solid-state imaging device. In the latter case, the signalcharges are transferred in the vertical direction by a vertical transferregister having CCD-type structure, and the signal charges aretransferred in the horizontal direction by a horizontal transferregister to be amplified, so that a pixel signal (image signal) isoutput. In addition, the present disclosure is not limited to overallcolumn-type solid-state imaging devices where pixels are formed in atwo-dimensional matrix shape and column signal processing circuits arearranged for the respective pixel columns. Furthermore, in some cases,the selection transistors may be omitted.

Furthermore, the imaging element and the stacked-type imaging element ofthe present disclosure are not limited to the application to thesolid-state imaging device which detects a distribution of the incidentlight amount of visible light to image the distribution as an image, butthe imaging element and the stacked-type imaging element of the presentdisclosure may also be applied to a solid-state imaging device whichimages a distribution of incident amount of infrared ray, X-ray,particles, or the like as an image. In addition, in a broad sense, theimaging element and the stacked-type imaging element of the presentdisclosure may be applied to overall solid-state imaging devices(physical quantity distribution detection devices) such as a fingerprintdetection sensor which detects a distribution of another physicalquantity such as pressure or electrostatic capacitance to image thedistribution as an image.

Furthermore, the present disclosure is not limited to a solid-stateimaging device which scans the unit pixels of the imaging regionsequentially in unit of a row to read out pixel signals from the unitpixels. The present disclosure may be applied to an X-Y address typesolid-state imaging device which arbitrarily selects pixels in unit of apixel and reads out pixel signals from select pixels in unit of a pixel.The solid-state imaging device may be formed as one chip, or thesolid-state imaging device may be formed in a module shape having animaging function where an imaging region, a driving circuit, or anoptical system is collectively packaged.

In addition, the present disclosure is not limited to the application tothe solid-state imaging device, but the present disclosure may beapplied to an imaging device. Herein, the imaging device denotes acamera system such as a digital still camera or a video camera or anelectronic apparatus such as a mobile phone having an imaging function.In some cases, the present disclosure may be implemented as amodule-shaped form which is to be mounted on an electronic apparatus,that is, a camera module.

An example where a solid-state imaging device 201 configured with theimaging element or the stacked-type imaging element of the presentdisclosure is used for an electronic apparatus (camera) 200 isillustrated in a conceptual diagram of FIG. 48. The electronic apparatus200 includes a solid-state imaging device 201, an optical lens 210, ashutter device 211, a driving circuit 212, and a signal processingcircuit 213. The optical lens 210 forms an image of image light(incident light) from a subject on an imaging place of the solid-stateimaging device 201. Therefore, signal charges are stored in thesolid-state imaging device 201 for a certain period. The shutter device211 controls a light-illuminating period and a light-shielding periodfor the solid-state imaging device 201. The driving circuit 212 suppliesdriving signals for controlling a transfer operation of the solid-stateimaging device 201 and a shutter operation of the shutter device 211.According to the driving signal (timing signal) supplied from thedriving circuit 212, signal transfer of the solid-state imaging device201 is performed. The signal processing circuit 213performs varioussignal processes. An image signal, which is subject to the signalprocesses, is stored in a storage medium such as a memory or is outputto a monitor. In the electronic apparatus 200, since pixel size andtransfer efficiency of the solid-state imaging device 201 are improved,it is possible to achieve the electronic apparatus 200 of which pixelcharacteristics are improved. The electronic apparatus 200 to which thesolid-state imaging device 201 can be applied is not limited to thecamera, but the electronic apparatus can be applied to an imaging devicesuch as a digital still camera or a camera module for a mobile apparatussuch as a mobile phone.

It should be understood by those skilled in the art that variousmodifications, combinations, sub-combinations and alterations may occurdepending on design requirements and other factors insofar as they arewithin the scope of the appended claims or the equivalents thereof.

Further, for example, the present technology can have the followingconfigurations.

(1) An imaging device including:

a substrate including a first photoelectric conversion unit; and asecond photoelectric conversion unit at a light-incident side of thesubstrate, the second photoelectric conversion unit including: aphotoelectric conversion layer, a first electrode, a second electrodeabove the photoelectric conversion layer, a third electrode, and aninsulating material between the third electrode and the photoelectricconversion layer, wherein a portion of the insulating material isbetween the first electrode and the third electrode.

(2) The imaging device according to (1) above, further including a firstregion of the insulating material between the third electrode and thephotoelectric conversion layer, a second region of the insulatingmaterial between the third electrode and the first electrode, whereinthe second region of the insulating material includes a first insulatinglayer including the insulating material and a second insulating layerincluding the insulating material, and wherein the first insulatingmaterial is stacked on the second insulating material.

(3) The imaging device according to (2) above, wherein a portion of thefirst insulating layer in the second region is between the firstelectrode and the photoelectric conversion layer.

(4) The imaging device according to (3) above, wherein the first regionand the second region include a different number of insulating layersincluding the insulating material.

(5) The imaging device according to any one of (1) to (4) above, furtherincluding a transfer control electrode between the first electrode andthe third electrode.

(6) The imaging device according to (5) above, wherein during a chargestorage operation, a potential applied to the transfer control electrodeis less than a potential applied to the third electrode.

(7) The imaging device according to any one of (5) to (6) above, whereinthe substrate includes a third photoelectric conversion unit, andwherein each of the first, second, and third photoelectric conversionunits are coupled to separate signal lines.

(8) The imaging device according to any one of (1) to (7) above, furtherincluding a charge ejection electrode separate and apart from the firstelectrode and the third electrode, wherein the photoelectric conversionlayer contacts the charge ejection electrode.

(9) The imaging device according to (8) above, wherein the chargeejection electrode surrounds the first electrode and the thirdelectrode.

(10) The imaging device according to any one of (1) to (9) above,further including a plurality of third electrode segments.

(11) The imaging device according to (10) above, wherein a potential ofa third electrode segment located at a position closest to the firstelectrode is greater than a potential of a third electrode segmentlocated at a position farthest from the first electrode.

(12) The imaging device according to any one of (1) to (11) above,wherein the photoelectric conversion layer includes a stacked layerstructure including a lower semiconductor layer and an upperphotoelectric conversion layer.

(13) The imaging device according to (12) above, wherein a materialcomposition of the lower semiconductor layer located above the thirdelectrode is different from a material composition of the lowersemiconductor layer located above the first electrode.

(14) The imaging device according to any one of (12) to (13) above,wherein the lower semiconductor layer includes an oxide includingindium.

(15) The imaging device according to any one of (1) to (14) above,wherein during a charge storage period, a potential applied to the thirdelectrode is greater than a potential applied to the first electrode.

(16) The imaging device according to any one of (1) to (15) above,wherein at least a part of the insulating material is disposed above thefirst electrode.

(17) The imaging device according to (16) above, wherein a thickness ofthe insulating material between the upper surface of the first electrodeand the photoelectric conversion layer increases at a third electrodeside of the first electrode as a distance between the first electrodeand the third electrode decreases.

(18) The imaging device according to any one of (1) to (17) above,wherein the imaging device is a back-illuminated type imaging device.

(19) An electronic apparatus including: an imaging device including: asubstrate including a first photoelectric conversion unit, and a secondphotoelectric conversion unit at a light-incident side of the substrate,the second photoelectric conversion unit including: a photoelectricconversion layer, a first electrode, a second electrode above thephotoelectric conversion layer, a third electrode, and an insulatingmaterial between the third electrode and the photoelectric conversionlayer, wherein a portion of the insulating material is between the firstelectrode and the third electrode, a lens configured to direct lightonto a surface of the imaging device, and circuitry configured tocontrol output signals from the imaging device.

(20) A method of driving an imaging device, the method including:applying a first potential to a charge storage electrode during acharging period; applying a second potential to a first electrode duringa charging period, wherein the first potential is greater than thesecond potential, applying a third potential to the charge storageelectrode during a charge transfer period, and

applying a fourth potential to the first electrode during the chargetransfer period, wherein the fourth potential is greater than the thirdpotential, and wherein, the imaging device includes: a substrateincluding a first photoelectric conversion unit, and a secondphotoelectric conversion unit at a light-incident side of the substrate,the second photoelectric conversion unit including: a photoelectricconversion layer, the first electrode,

a second electrode above the photoelectric conversion layer,

the charge storage electrode, and an insulating material between thecharge storage electrode and the photoelectric conversion layer, whereina portion of the insulating material is between the first electrode andthe charge storage electrode.

(A01) «Imaging Element»

An imaging element including

a photoelectric conversion unit configured by stacking a firstelectrode, a photoelectric conversion layer, and a second electrode,

wherein the photoelectric conversion unit further includes a chargestorage electrode which is arranged to be separated from the firstelectrode and is arranged to face the photoelectric conversion layerthrough an insulating layer.

(A02)

The imaging element according to (A01), further including asemiconductor substrate,

wherein the photoelectric conversion unit is arranged above thesemiconductor substrate.

(A03)

The imaging element according to (A01) or (A02), wherein the firstelectrode extends in an opening portion provided to the insulating layerto be connected to the photoelectric conversion layer.

(A04)

The imaging element according to (A01) or (A02), wherein thephotoelectric conversion layer extends in an opening portion provided tothe insulating layer to be connected to the first electrode.

(A05)

The imaging element according to (A04),

wherein an edge of a top surface of the first electrode is covered withthe insulating layer,

the first electrode is exposed to a bottom surface of the openingportion, and

when a surface of the insulating layer being in contact with the topsurface of the first electrode is defined by a first surface and asurface of the insulating layer being in contact with a portion of thephotoelectric conversion layer facing the charge storage electrode isdefined by a second surface, a side surface of the opening portion has aslope expanding from the first surface toward the second surface.

(A06)

The imaging element according to (A05), wherein the side surface of theopening portion having the slope expanding from the first surface towardthe second surface is located in a charge storage electrode side.

(A07) «Control of Potentials of First Electrode and Charge StorageElectrode»

The imaging element according to any one of (A01) to (A06), furtherincluding a control unit which is provided to a semiconductor substrateand includes a driving circuit,

wherein the first electrode and the charge storage electrode areconnected to the driving circuit,

in a charge storage period, from the driving circuit, a potential V₁₁ isapplied to the first electrode, and a potential V₁₂ is applied to thecharge storage electrode, so that charges are stored in thephotoelectric conversion layer, and

in a charge transfer period, from the driving circuit, a potential V₂₁is applied to the first electrode, and a potential V₂₂ is applied to thecharge storage electrode, so that the charges stored in thephotoelectric conversion layer are read out to the control unit throughthe first electrode,

in the case where a potential of the first electrode is higher than apotential of the second electrode,

V₁₂≥V₁₁, and V₂₂<V₂₁, and

in the case where the potential of the first electrode is lower than thepotential of the second electrode,

V₁₂≤V₁₁ and V₂₂>V₂₁.

(A08) «Transfer Control Electrode»

The imaging element according to any one of (A01) to (A06), furtherincluding a transfer control electrode which is arranged between thefirst electrode and the charge storage electrode to be separated fromthe first electrode and the charge storage electrode and is arranged toface the photoelectric conversion layer through the insulating layer.

(A09) «Control of Potentials of First Electrode, Charge StorageElectrode, and Transfer Control Electrode»

The imaging element according to (A08), further including a control unitwhich is provided to a semiconductor substrate and includes a drivingcircuit,

wherein the first electrode, the charge storage electrode, and thetransfer control electrode are connected to the driving circuit,

in a charge storage period, from the driving circuit, a potential V₁₁ isapplied to the first electrode, a potential V₁₂ is applied to the chargestorage electrode, and a potential V₁₃ is applied to the transfercontrol electrode, so that charges are stored in the photoelectricconversion layer, and

in a charge transfer period, from the driving circuit, a potential V₂₁is applied to the first electrode, a potential V₂₂ is applied to thecharge storage electrode, and a potential V₂₃ is applied to the transfercontrol electrode, so that the charges stored in the photoelectricconversion layer are read out to the control unit through the firstelectrode,

in the case where a potential of the first electrode is higher than apotential of the second electrode,

V₁₂>V₁₃ and V₂₂≤V₂₃≤V₂₁, and

in the case where the potential of the first electrode is lower than thepotential of the second electrode,

V₁₂<V₁₃ and V₂₂≥V₂₃≥V₂₁.

(A10) «Charge Ejection Electrode»

The imaging element according to any one of (A01) to (A09), furtherincluding a charge ejection electrode which is connected to thephotoelectric conversion layer and is arranged to be separated from thefirst electrode and the charge storage electrode.

(A11)

The imaging element according to (A10), wherein the charge ejectionelectrode is arranged to surround the first electrode and the chargestorage electrode.

(A12)

The imaging element according to (A10) or (A11),

wherein the photoelectric conversion layer extends in a second openingportion provided to the insulating layer to be connected to the chargeejection electrode,

an edge of a top surface of the charge ejection electrode is coveredwith the insulating layer,

the charge ejection electrode is exposed to a bottom surface of thesecond opening portion, and

when a surface of the insulating layer being in contact with the topsurface of the charge ejection electrode is defined by a third surfaceand a surface of the insulating layer being in contact with a portion ofthe photoelectric conversion layer facing the charge storage electrodeis defined by a second surface, a side surface of the second openingportion has a slope expending from the third surface toward the secondsurface.

(A13) «Control of Potentials of First Electrode, Charge StorageElectrode, and Charge Ejection Electrode»

The imaging element according to any one of (A10) to (A12), furtherincluding a control unit which is provided to the semiconductorsubstrate and has a driving circuit,

wherein the first electrode, the charge storage electrode, and thecharge ejection electrode are connected to the driving circuit,

in a charge storage period, from the driving circuit, a potential V₁₁ isapplied to the first electrode, a potential V₁₂ is applied to the chargestorage electrode, and a potential V₁₄ is applied to the charge ejectionelectrode, so that charges are stored in the photoelectric conversionlayer,

in a charge transfer period, from the driving circuit, a potential V₂₁is applied to the first electrode, a potential V₂₂ is applied to thecharge storage electrode, and a potential V₂₄ is applied to the chargeejection electrode, so that the charges stored in the photoelectricconversion layer are read out to the control unit through the firstelectrode,

in the case where a potential of the first electrode is higher than apotential of the second electrode,

V₁₄>V₁₁ and V₂₄<V₂₁, and

in the case where the potential of the first electrode is lower than thepotential of the second electrode,

V₁₄<V₁₁ and V₂₄>V₂₁.

(A14) «Charge Storage Electrode Segment»

The imaging element according to any one of (A01) to (A13), wherein thecharge storage electrode is configured with a plurality of chargestorage electrode segments.

(A15)

The imaging element according to (A14), wherein in the case where apotential of the first electrode is higher than a potential of thesecond electrode, in a charge transfer period, a potential applied tothe charge storage electrode segment located at the position closest tothe first electrode is higher than a potential applied to the chargestorage electrode segment located at the position farthest from thefirst electrode, and in the case where the potential of the firstelectrode is lower than the potential of the second electrode, in thecharge transfer period, the potential applied to the charge storageelectrode segment located at the position closest to the first electrodeis lower than the potential applied to the charge storage electrodesegment located at the position farthest from the first electrode.

(B01)

The imaging element according to any one of (A01) to (A15),

wherein at least a floating diffusion layer and an amplificationtransistor constituting a control unit are provided to a semiconductorsubstrate, and

the first electrode is connected to the floating diffusion layer and agate portion of the amplification transistor.

(B02)

The imaging element according to (B01),

wherein a reset transistor and a selection transistor constituting thecontrol unit are further provided to the semiconductor substrate,

the floating diffusion layer is connected to one source/drain region ofthe reset transistor, and

one source/drain region of the amplification transistor is connected toone source/drain region of the selection transistor, and the othersource/drain region of the selection transistor is connected to a signalline.

(B03)

The imaging element according to any one of (A01) to (B02), wherein thecharge storage electrode is larger than the first electrode.

(B04)

The imaging element according to any one of (A01) to (B03), whereinlight is incident from a second electrode side, and a light-shieldinglayer is formed in a light incidence side of the second electrode.

(B05)

The imaging element according to any one of (A01) to (B03), whereinlight is incident from a second electrode side, and light is notincident on the first electrode.

(B06)

The imaging element according to (B05), wherein a light-shielding layeris formed above the first electrode as a light incidence side of thesecond electrode.

(B07)

The imaging element according to (B05),

wherein an on-chip microlens is provided above the charge storageelectrode and the second electrode, and

light incident on the on-chip microlens is collected in the chargestorage electrode.

(C01) «Stacked-Type Imaging Element»

A stacked-type imaging element including at least one imaging elementaccording to any one of (A01) to (B07).

(D01) «Solid-State Imaging Device . . . First Embodiment»

A solid-state imaging device including a plurality of the imagingelements according to any one of (A01) to (B04).

(D02) «Solid-State Imaging Device . . . Second Embodiment»

A solid-state imaging device including a plurality of the stacked-typeimaging elements according to (C01).

(E01) «Driving Method for Solid-State Imaging Device»

A driving method for a solid-state imaging device having a plurality ofimaging elements having a structure where

a photoelectric conversion unit configured by stacking a firstelectrode, a photoelectric conversion layer, and a second electrode isincluded,

the photoelectric conversion unit further includes a charge storageelectrode which is arranged to be separated from the first electrode andis arranged to face the photoelectric conversion layer through aninsulating layer, and

light is incident from a second electrode side, and light is notincident on the first electrode, the driving method includingrepetitively:

in all the imaging elements, at one time, storing charges in thephotoelectric conversion layer, and ejecting the charges of the firstelectrode to the outside;

in all the imaging elements, at one time, transferring the chargesstored in the photoelectric conversion layer to the first electrode; and

after the completion of transfer, sequentially, reading out the chargestransferred to the first electrodes in the respective imaging elements.

REFERENCE SIGNS LIST

-   11 First electrode-   12 Charge storage electrode-   12A, 12B, 12C Charge storage electrode segment-   13, 13A, 13B Transfer control electrode (charge transfer electrode)-   14 Charge ejection electrode-   15 Photoelectric conversion layer-   16 Second electrode-   41 n-type semiconductor region constituting second imaging element-   43 n-type semiconductor region constituting third imaging element-   42, 44, 73 p+ layer-   FD₁, FD₂, FD₃, 45C, 46C Floating diffusion layer-   TR1 _(amp) Amplification transistor-   TR1 _(rst) Reset transistor-   TR1 _(sel) Selection transistor-   51 Gate portion of reset transistor TR1 _(rst)-   51A Channel forming region of reset transistor TR1 _(rst)-   51B, 51C Source/drain region of reset transistor TR1 _(rst)-   52 Gate portion of amplification transistor TR1 _(amp)-   52A Channel forming region of amplification transistor TR1 _(amp)-   52B, 52C Source/drain region of amplification transistor TR1 _(amp)-   53 Gate portion of selection transistor TR1 _(sel)-   53A Channel forming region of selection transistor TR1 _(sel)-   53B, 53C Source/drain region of selection transistor TR1 _(sel)-   TR2 _(trs) Transfer transistor-   45 Gate portion of transfer transistor-   TR2 _(rst) Reset transistor-   TR2 _(amp) Amplification transistor-   TR2 _(sel) Selection transistor-   TR3 _(trs) Transfer transistor-   46 Gate portion of transfer transistor-   TR3 _(rst) Reset transistor-   TR3 _(amp) Amplification transistor-   TR3 _(sel) Selection transistor-   V_(DD) Power source-   RST₁, RST₂, RST₃ Reset line-   SEL₁, SEL₂, SEL₃ Select line-   117, VSL₁, VSL₂, VSL₃ Signal line-   TG₂, TG₃ Transfer gate line-   V_(OA), V_(OT), V_(OU) Wire line-   61 Contact hole portion-   62 Wire line layer-   63, 64, 68A Pad portion-   65, 68B Connection hole-   66, 67, 69 Connection portion-   70 Semiconductor substrate-   70A First surface (front surface) semiconductor substrate-   70B Second surface (back surface) semiconductor substrate-   71 Element isolation region-   72 Oxide film-   74 HfO₂ film-   75 Insulating film-   76 Interlayer insulating layer-   77, 78, 81 Interlayer insulating layer-   82 Insulating layer-   82 a First surface of insulating layer-   82 b Second surface of insulating layer-   82 c Third surface of insulating layer-   83 Protective layer-   84, 84A, 84B, 84C Opening portion-   85, 85A Second opening portion-   90 On-chip microlens-   91 Various components of imaging element located below interlayer    insulating layer 81-   92 Light-shielding layer-   100 Solid-state imaging device-   101 Stacked-type imaging element-   111 Imaging region-   112 Vertical driving circuit-   113 Column signal processing circuit-   114 Horizontal driving circuit-   115 Output circuit-   116 Driving control circuit-   118 Horizontal signal line-   200 Electronic apparatus (camera)-   201 Solid-state imaging device-   210 Optical lens-   211 Shutter device-   212 Driving circuit-   213 Signal processing circuit

1. An imaging device comprising: a plurality of pixels, each pixel ofthe plurality of pixels including: a first photoelectric conversion unitdisposed in a substrate, and a second photoelectric conversion unitdisposed above and at a light-incident side of the substrate, the secondphotoelectric conversion unit including: a first electrode, aphotoelectric conversion layer above the first electrode, a secondelectrode above the photoelectric conversion layer, a third electrodedisposed at a same layer as the first electrode, and an insulatingmaterial between the third electrode and the photoelectric conversionlayer, wherein a portion of the insulating material is between the firstelectrode and the third electrode.
 2. The imaging device according toclaim 1, further comprising: a first region of the insulating materialbetween the third electrode and the photoelectric conversion layer; anda second region of the insulating material between the third electrodeand the first electrode, wherein the second region of the insulatingmaterial includes a first insulating layer including the insulatingmaterial and a second insulating layer including the insulatingmaterial, and wherein the first insulating material is stacked on thesecond insulating material.
 3. The imaging device according to claim 2,wherein a portion of the first insulating layer in the second region isbetween the first electrode and the photoelectric conversion layer. 4.The imaging device according to claim 2, wherein the first region andthe second region include a different number of insulating layersincluding the insulating material.
 5. The imaging device according toclaim 1, further comprising: a transfer control electrode between thefirst electrode and the third electrode.
 6. The imaging device accordingto claim 5, wherein during a charge storage operation, a potentialapplied to the transfer control electrode is less than a potentialapplied to the third electrode.
 7. The imaging device according to claim5, wherein the substrate includes a third photoelectric conversion unit,and wherein each of the second, first, and third photoelectricconversion units are coupled to separate signal lines.
 8. The imagingdevice according to claim 1, further comprising: a charge ejectionelectrode separate and apart from the first electrode and the thirdelectrode, wherein the photoelectric conversion layer contacts thecharge ejection electrode.
 9. The imaging device according to claim 8,wherein the charge ejection electrode is disposed at the same layer asthe first electrode and the third electrode, and wherein the chargeejection electrode surrounds the first electrode and the thirdelectrode.
 10. The imaging device according to claim 1, furthercomprising: a plurality of third electrode segments.
 11. The imagingdevice according to claim 10, wherein a potential of a third electrodesegment located at a position closest to the first electrode is greaterthan a potential of a third electrode segment located at a positionfarthest from the first electrode.
 12. The imaging device according toclaim 1, wherein the photoelectric conversion layer includes a stackedlayer structure of a plurality of layers.
 13. The imaging deviceaccording to claim 12, wherein a first layer of the stacked layerstructure is an oxide semiconductor layer and a second layer of thestacked layer structure is a photoelectric conversion layer.
 14. Theimaging device according to claim 12, wherein the first layer of thestacked structure includes an oxide including indium.
 15. The imagingdevice according to claim 1, wherein during a charge storage period, apotential applied to the third electrode is greater than a potentialapplied to the first electrode.
 16. The imaging device according toclaim 1, wherein at least a part of the insulating material is disposedabove the first electrode.
 17. The imaging device according to claim 16,wherein a thickness of the insulating material between the upper surfaceof the first electrode and the photoelectric conversion layer increasesat a third electrode side of the first electrode as a distance betweenthe first electrode and the third electrode decreases.
 18. The imagingdevice according to claim 1, wherein a thickness of the third electrodeis substantially the same as a thickness of the first electrode.
 19. Anelectronic apparatus comprising: an imaging device including a pluralityof pixels, each pixel of the plurality of pixels including: a firstphotoelectric conversion unit disposed in a substrate, and a secondphotoelectric conversion unit disposed above and at a light-incidentside of the substrate, the second photoelectric conversion unitincluding: a first electrode, a photoelectric conversion layer above thefirst electrode, a second electrode above the photoelectric conversionlayer, a third electrode disposed at a same layer as the firstelectrode, and an insulating material between the third electrode andthe photoelectric conversion layer, wherein a portion of the insulatingmaterial is between the first electrode and the third electrode; and alens configured to direct light onto a surface of the imaging device;and circuitry configured to control output signals from the imagingdevice.
 20. A method of driving an imaging device, the methodcomprising: applying a first potential to a charge storage electrodeduring a charging period; applying a second potential to a firstelectrode during a charging period, wherein the first potential isgreater than the second potential; applying a third potential to thecharge storage electrode during a charge transfer period; and applying afourth potential to the first electrode during the charge transferperiod, wherein the fourth potential is greater than the thirdpotential, and wherein, the imaging device includes a plurality ofpixels, each pixel of the plurality of pixels including: a firstphotoelectric conversion unit disposed in a substrate; and a secondphotoelectric conversion unit disposed above and at a light-incidentside of the substrate, the second photoelectric conversion unitincluding: the first electrode, a photoelectric conversion layer abovethe first electrode, a second electrode above the photoelectricconversion layer, the charge storage electrode disposed at a same layeras the first electrode, and an insulating material between the chargestorage electrode and the photoelectric conversion layer, wherein aportion of the insulating material is between the first electrode andthe charge storage electrode.